Synthesis of cyclic non-benzene polycyclic aromatic hydrocarbons based on oxidative coupling reaction of carbon-hydrogen bond and its application

Abstract

This invention provides the synthesis and applications of cyclic non-benzene polycyclic aromatic hydrocarbons (PAHs) based on carbon-hydrogen bond oxidative coupling reactions. This invention successfully synthesizes a class of cyclic PAHs via carbon-hydrogen bond oxidative coupling reactions, and derivatizes their carbonyl functional groups using representative compounds, ultimately obtaining open-shell cyclic PAHs. Their applications are then explored. This method has advantages such as simplicity, efficiency, effective shortening of reaction routes, and the ability to synthesize cyclic non-benzene PAHs that are unattainable by traditional methods. The cyclic non-benzene PAH molecules synthesized by this invention have the potential to serve as photoelectric and electromagnetic functional materials.

Description

Technical Field

[0001] This invention relates to the development, synthesis method and application of a class of cyclic non-benzene polycyclic aromatic hydrocarbons, belonging to the field of organic optoelectronic materials. Background Technology

[0002] Compared to benzene-type polycyclic aromatic hydrocarbons (PAHs) containing only six-membered ring systems, non-benzene PAHs containing five-membered and seven-membered ring systems possess unique chemical structures, energy level structures, and packing arrangements, thus exhibiting unique photochemical, electromagnetic, and other physicochemical properties. Therefore, non-benzene PAHs have received widespread attention and research from scientists in recent years.

[0003] Using a bottom-up synthetic approach, scientists have designed and synthesized non-benzene polycyclic aromatic hydrocarbons (NPHs) with a rich variety of geometries, such as planar, bilayer, bowl-shaped, saddle-shaped, and helical NPHs. Among these, cyclic NPHs are extremely rare. Compared to the above configurations, cyclic NPHs possess more three-dimensional internal cavities, exhibiting more unique electronic structures and chiral optical characteristics. Therefore, designing and synthesizing cyclic NPHs and exploring their properties and functions is of great significance for deepening our understanding of the structure-activity relationship of this class of compounds and expanding the range of organic optoelectronic functional materials.

[0004] The lack of research on non-benzene polycyclic aromatic hydrocarbons with cyclic configurations is mainly due to the limited availability of synthetic methods.

[0005] Oxidative coupling reactions involving carbon-hydrogen bonds are concise and efficient, effectively shortening reaction routes. However, this reaction is typically applicable to the construction of intramolecular six-membered rings in benzene-type polycyclic aromatic hydrocarbons (PAHs) and the linkage of intermolecular segments in individual non-benzene PAHs. The synthesis of cyclic non-benzene PAHs through multiple intermolecular carbon-hydrogen bond oxidative coupling reactions has not been reported. Therefore, the ability to utilize carbon-hydrogen bond oxidative coupling reactions to achieve multiple linkages between non-benzene PAH segments and synthesize cyclic non-benzene PAHs is of great significance for expanding the application scope of this reaction and for studying the structure-activity relationships of cyclic non-benzene PAHs. Summary of the Invention

[0006] One of the objectives of this invention is to provide a class of cyclic non-benzene polycyclic aromatic hydrocarbons and a method for preparing them.

[0007] The present invention provides a class of cyclic non-benzene polycyclic aromatic hydrocarbons, the structural formula of which is shown in Formula I:

[0008]

[0009] In Formula I above, the conjugated unit Ar is independently selected from either a substituted or unsubstituted benzene-type polycyclic aromatic hydrocarbon segment fused at the edge of a five-membered ring or a substituted or unsubstituted non-benzene-type polycyclic aromatic hydrocarbon segment fused at the edge of a five-membered ring;

[0010] The benzene-type polycyclic aromatic hydrocarbon fragment is independently selected from any one of the following: benzene ring, biphenyl, fluorenyl, naphthyl ring, anthracene ring, pyrene ring, perylene ring, thiophene ring, pyridine ring, pyrrole ring, furan ring, and carbazole ring;

[0011] The substituents in the substituted benzene-type polycyclic aromatic hydrocarbon fragment are substituted in any number and at any position in the benzene-type polycyclic aromatic hydrocarbon;

[0012] The substituents may be independently selected from any one of fluorine, chlorine, bromine, iodine, C1-C10 haloalkyl (such as trifluoromethyl), nitro, ester, carboxyl, C1-C18 (specifically C4-C10, C4-C8, more specifically C4) straight-chain alkyl or branched alkyl, C1-C18 (specifically C4-C10, C4-C8, more specifically C6) straight-chain or branched alkoxy, C1-C18 (specifically C4-C10, C4-C8, more specifically C4) straight-chain or branched alkylamino, trimethylsilyl (TMS), triisopropylsilyl (TIPS), and tert-butyldimethylsilyl (TBDMS);

[0013] The non-benzene polycyclic aromatic hydrocarbon fragment is independently selected from any one of benzocycloheptenene, dibenzocycloheptenone, and dibenzocyclooctene;

[0014] In Equation I above, the bridging unit π is independently selected from either benzene-type polycyclic aromatic hydrocarbon segments or non-benzene-type polycyclic aromatic hydrocarbon segments;

[0015] Specifically, the conjugated unit Ar in Formula I above can be either a naphthalene ring fused at the edge of a five-membered ring or a dibenzocycloheptenone fused at the edge of a five-membered ring;

[0016] The bridging unit π in Equation I above can be either a benzene ring or a naphthalene ring.

[0017] Furthermore, the three compounds shown in Formula I above can specifically be compounds with the following structures:

[0018]

[0019] The compound shown in Formula I above is prepared by a method comprising the following steps: reacting the compound shown in Formula II with an oxidative coupling reaction in an organic solvent in the presence of an oxidant and an acid to obtain the compound shown in Formula I.

[0020]

[0021] In Formula II above, the conjugated unit Ar is independently selected from either a substituted or unsubstituted benzene-type polycyclic aromatic hydrocarbon segment fused at the edge of a five-membered ring or a substituted or unsubstituted non-benzene-type polycyclic aromatic hydrocarbon segment fused at the edge of a five-membered ring;

[0022] The benzene-type polycyclic aromatic hydrocarbon fragment is independently selected from any one of the following: benzene ring, biphenyl, fluorenyl, naphthalene ring, anthracene ring, pyrene ring, perylene ring, thiophene ring, pyridine ring, pyrrole ring, furan ring, and carbazole ring.

[0023] The substituents in the substituted benzene-type polycyclic aromatic hydrocarbon fragment are substituted in any number and at any position in the benzene-type polycyclic aromatic hydrocarbon;

[0024] The substituents may be independently selected from any one of fluorine, chlorine, bromine, iodine, C1-C10 haloalkyl (such as trifluoromethyl), nitro, ester, carboxyl, C1-C18 (specifically C4-C10, C4-C8, more specifically C4) straight-chain alkyl or branched alkyl, C1-C18 (specifically C4-C10, C4-C8, more specifically C6) straight-chain or branched alkoxy, C1-C18 (specifically C4-C10, C4-C8, more specifically C4) straight-chain or branched alkylamino, trimethylsilyl (TMS), triisopropylsilyl (TIPS), and tert-butyldimethylsilyl (TBDMS);

[0025] In Equation II above, the bridging unit π is independently selected from either benzene-type polycyclic aromatic hydrocarbon segments or non-benzene-type polycyclic aromatic hydrocarbon segments.

[0026] The conjugated unit Ar in Formula II above can be either a naphthalene ring fused at the edge of a five-membered ring or a dibenzocycloheptenone fused at the edge of a five-membered ring.

[0027] The bridging unit π in Equation II above can be either a benzene ring or a naphthalene ring.

[0028] In Formula II above, R can specifically be trimethylsilyl (TMS) or a hydrogen atom.

[0029] The three compounds shown in Formula II above can specifically be compounds with the following structures:

[0030]

[0031] The reaction is carried out in a nitrogen or air atmosphere;

[0032] The temperature of the oxidative coupling reaction can be 0-80℃, specifically 25℃;

[0033] The oxidative coupling reaction can take 0.5-24 hours, specifically 1 hour.

[0034] The organic solvent may be at least one of dichloromethane, chloroform, tetrahydrofuran, toluene, o-xylene, o-dichlorobenzene and N,N-dimethylformamide, specifically dichloromethane;

[0035] The oxidant may be selected from at least one of ferric chloride, lead dioxide, manganese dioxide, benzoquinone, o-tetrachlorobenzoquinone, p-tetrachlorobenzoquinone, 2,3-dichloro-5,6-dicyanobenzoquinone, 3,5-di-tert-butyl-O-catechol, and oxygen, specifically 2,3-dichloro-5,6-dicyanobenzoquinone.

[0036] The acid may be selected from at least one of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, and methanesulfonic acid, specifically trifluoromethanesulfonic acid;

[0037] The molar ratio of the compound, oxidant and acid shown in Formula II can be 1:1-30:10-200, specifically 1:4:50.

[0038] After the reaction is completed, the following processing steps are also included: after the reaction is completed, hydrazine hydrate is slowly added dropwise to the system for quenching, and then a large amount of water is added to the system for extraction three times. The organic phase is separated by liquid-liquid extraction, evaporated to dryness, and then separated and purified by column chromatography, wherein dichloromethane / ethyl acetate (100:1 to 10:1) is used as the eluent to obtain the compound shown in Formula I.

[0039] This invention explores the application of the compound described in Formula I.

[0040] The carbonyl functional group was derivatized to obtain an open-shell cyclic non-benzene polycyclic aromatic hydrocarbon compound, the structural formula of which is shown in Formula V:

[0041]

[0042]

[0043] In Formula V above, R1 is independently selected from any one of the following: C1-C10 haloalkyl (such as trifluoromethyl, dichloromethyl), cyanomethyl, C1-C10 (specifically C1-C5, more specifically C1 or C3) straight-chain alkyl or branched-chain alkyl, C2-C10 (specifically C1-C5, more specifically C1 or C3) straight-chain alkenyl or branched-chain alkenyl, C1-C10 (specifically C1-C5, more specifically C1 or C3) straight-chain alkynyl or branched-chain alkynyl, and aromatic rings containing substituents.

[0044] The aromatic ring is independently selected from any one of the following: benzene ring, naphthalene ring, anthracene ring, pyrene ring, perylene ring, and carbazole ring.

[0045] The substituents in the substituted aromatic ring are substituted in any number and at any position on the aromatic ring;

[0046] The substituents may be independently selected from any one of fluorine, chlorine, bromine, C1-C10 haloalkyl (such as trifluoromethyl), nitro, C1-C10 (specifically C1-C5, more specifically C1) straight-chain alkyl or branched alkyl, C1-C10 (specifically C1-C5, more specifically C1) straight-chain or branched alkoxy, trimethylsilyl (TMS), triisopropylsilyl (TIPS) and tert-butyldimethylsilyl (TBDMS);

[0047] R1 in formula V above can specifically be 2,4,6-trimethylphenyl.

[0048] In Equation V above, the bridging unit π is independently selected from either benzene-type polycyclic aromatic hydrocarbon segments or non-benzene-type polycyclic aromatic hydrocarbon segments.

[0049] The bridging unit π in Equation V above can specifically be a benzene ring.

[0050] The compound shown in Formula V above is prepared by a method comprising the following steps: oxidizing the compound shown in Formula VI in an organic solvent in the presence of an oxidizing agent to obtain the compound shown in Formula V.

[0051]

[0052] R1 in Formula VI above can specifically be a 2,4,6-trimethylbenzene ring.

[0053] The bridging unit π in Equation VI above can specifically be a benzene ring.

[0054] The reaction is carried out in a nitrogen or air atmosphere;

[0055] The reaction temperature can be 25-150℃, specifically 90℃;

[0056] The reaction time can be 0.5-5 hours, specifically 1 hour;

[0057] The organic solvent may be at least one selected from dichloromethane, chloroform, tetrahydrofuran, toluene, o-xylene, o-dichlorobenzene, dichloromethane, tetrachloroethane, and N,N-dimethylformamide, specifically toluene;

[0058] The oxidant may be selected from at least one of oxygen, benzoquinone, o-tetrachlorobenzoquinone, p-tetrachlorobenzoquinone, 2,3-dichloro-5,6-dicyanobenzoquinone, ferric chloride, silver nitrate, cerium ammonium nitrate, lead dioxide, manganese dioxide, 3,5-di-tert-butyl-O-catechol, copper chloride, and potassium persulfate, specifically 2,3-dichloro-5,6-dicyanobenzoquinone;

[0059] After the reaction is completed, the following processing steps are also included: after the reaction is completed, the solvent is removed by rotary evaporator, and then the system is separated and purified by column chromatography, wherein petroleum ether / dichloromethane (1:1 to 1:10) is used as the eluent to obtain the compound shown in Formula V.

[0060] The compound shown in Formula VI above is obtained by reducing the compound shown in Formula VII in the presence of stannous chloride (SnCl2) and concentrated hydrochloric acid.

[0061]

[0062] R1 in formula VII above can specifically be a 2,4,6-trimethylbenzene ring;

[0063] The bridging unit π in Equation VII above can specifically be a benzene ring.

[0064] The reaction is carried out in a nitrogen or air atmosphere;

[0065] The reaction temperature can be 0-80℃, specifically 0℃;

[0066] The reaction time can be 1-12 hours, specifically 1 hour;

[0067] The organic solvent may be at least one of chloroform, tetrahydrofuran, toluene, o-xylene, o-dichlorobenzene, tetrachloroethane and N,N-dimethylformamide, specifically tetrahydrofuran;

[0068] The molar ratio of the compound shown in Formula VII to stannous chloride can be 1:10-30, specifically 1:15;

[0069] After the reaction is completed, the following processing steps are also included: after the reaction is completed, water is added to the system to quench the reaction, and then dichloromethane and water are used for extraction to separate the organic phase. The solvent is removed by rotary evaporation, and then column chromatography is used for separation and purification, wherein petroleum ether / dichloromethane (5:1 to 1:1) is used as the eluent to obtain the compound shown in Formula VI.

[0070] The compound shown in Formula VII is obtained by the addition reaction of the compound shown in Formula I (such as compound 2 or compound 3) with the Grignard reagent shown in Formula VIII:

[0071] R1-MgBr formula VIII

[0072] In formula VIII above, R1 is independently selected from any one of the following: C1-C10 haloalkyl (such as trifluoromethyl, dichloromethyl), cyanomethyl, C1-C10 (specifically C1-C5, more specifically C1 or C3) straight-chain alkyl or branched-chain alkyl, C1-C10 (specifically C1-C5, more specifically C1 or C3) straight-chain alkenyl or branched-chain alkenyl, C1-C10 (specifically C1-C5, more specifically C1 or C3) straight-chain alkynyl or branched-chain alkynyl, and aromatic rings containing substituents.

[0073] The aromatic ring is independently selected from any one of the following: benzene ring, naphthalene ring, anthracene ring, pyrene ring, perylene ring, and carbazole ring.

[0074] The substituents in the substituted aromatic ring are substituted in any number and at any position on the aromatic ring;

[0075] The substituents may be independently selected from any one of fluorine, chlorine, bromine, C1-C10 haloalkyl (such as trifluoromethyl), nitro, C1-C10 (specifically C1-C5, more specifically C1) straight-chain alkyl or branched alkyl, C1-C10 (specifically C1-C5, more specifically C1) straight-chain or branched alkoxy, trimethylsilyl (TMS), triisopropylsilyl (TIPS) and tert-butyldimethylsilyl (TBDMS);

[0076] R1 in formula VIII above can specifically be a 2,4,6-trimethylbenzene ring.

[0077] The reaction is carried out in a nitrogen or air atmosphere;

[0078] The reaction temperature can be 0-80℃, specifically 0℃;

[0079] The reaction time can be 1-12 hours, specifically 4 hours;

[0080] The organic solvent may be at least one of chloroform, tetrahydrofuran, toluene, o-xylene, o-dichlorobenzene, tetrachloroethane and N,N-dimethylformamide, specifically tetrahydrofuran;

[0081] The molar ratio of the compound shown in Formula I and the compound shown in Formula VIII can be 1:10-80, specifically 1:40;

[0082] After the reaction is completed, the following processing steps are also included: after the reaction is completed, an aqueous solution of ammonium chloride is added to the system to quench the reaction, and then the organic phase is extracted with dichloromethane and water to separate the organic phase. The solvent is then removed by rotary evaporation to obtain the compound shown in Formula VII.

[0083] The applications of the compounds shown in Formulas I and V above in near-infrared absorption light detection, field-effect transistors, organic solar cells, organic light-emitting diodes, chiral optics, and nonlinear optics are also within the scope of protection of this invention.

[0084] The application of the compound shown in Formula V as a photoelectric and electromagnetic functional material also falls within the scope of protection of this invention.

[0085] The application of the compound shown in Formula V as a stable free radical magnetic material is also within the scope of protection of this invention.

[0086] The compound shown in Formula V is a free radical compound with open-shell properties, a strong spin distribution, and stability.

[0087] This invention successfully synthesized a class of cyclic non-benzene polycyclic aromatic hydrocarbons (PAHs) via carbon-hydrogen bond oxidative coupling reactions. Representative compounds were selected and their carbonyl functional groups were derivatized to obtain open-shell cyclic non-benzene PAHs, and their applications were explored. This method has advantages such as simplicity, efficiency, effective shortening of reaction routes, and the ability to synthesize cyclic non-benzene PAHs that are unavailable through traditional methods. The cyclic non-benzene PAHs synthesized by this invention all have the potential to serve as photoelectric and electromagnetic functional materials. Attached Figure Description

[0088] Figure 1 The reaction equations are for compounds (compounds 1, 2, and 3) described in Formula I in Example 1 of this invention.

[0089] Figure 2 The crystal structures of the compounds (compounds 1, 2, and 3) of Formula I in Example 1 are shown.

[0090] Figure 3 The UV-Vis absorption spectra of the compounds (compounds 1, 2, and 3) of Formula I in Example 1 in dichloromethane solution are shown.

[0091] Figure 4 The circular dichroism spectrum of the compounds (compounds 2 and 3) described in Formula I in Example 1 is shown.

[0092] Figure 5 The reaction equation for compound 13 (Formula V) in Example 5.

[0093] Figure 6 The variable-temperature 1H NMR spectrum of the compound (compound 13) of formula V in Example 5.

[0094] Figure 7 The electron paramagnetic resonance spectrum of the compound (compound 13) of formula V in Example 5 is shown.

[0095] Figure 8The UV-Vis absorption spectrum of compound 13 (Formula V) in Example 5, in dichloromethane solution at room temperature under sunlight, varies with time. Detailed Implementation

[0096] The present invention will now be described in further detail with reference to specific embodiments. The given embodiments are merely illustrative of the invention and not intended to limit its scope. The embodiments provided below can serve as a guide for further improvements by those skilled in the art and do not constitute a limitation on the invention in any way.

[0097] Unless otherwise specified, the experimental methods used in the following examples are conventional methods, performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Unless otherwise specified, the materials and reagents used in the following examples are commercially available.

[0098] Example 1: Synthesis of compounds (compounds 1, 2, and 3) of Formula I

[0099] Chemical reaction equations such as Figure 1 As shown, the specific reaction conditions are as follows:

[0100] Compound 7 of Formula III (500 mg, 1.85 mmol, 1.0 eq.), compound 9 of Formula IV (7.65 g, 37.0 mmol, 20.0 eq.), bis(dibenzylacetone)palladium (391 mg, 0.56 mmol, 30%), and 2-biscyclohexylphosphine-2',6'-dimethoxybiphenyl (304 mg, 0.74 mmol, 40%) were loaded into a reaction tube. After replacing the air in the system with nitrogen using the Shrek technique, 1,2-dimethylbenzene (40 mL) and triethylamine (3 mL) were injected. The system was placed in an oil bath at 110 °C and reacted for 12 h. After the reaction was stopped, the system was concentrated and separated by column chromatography with a petroleum ether:dichloromethane polarity of 5:1 to 1:1 to give compound 4 of Formula II (170 mg, yield 17.6%).

[0101] Compound 7 of Formula III (300 mg, 1.11 mmol, 1.0 eq.), compound 10 of Formula IV (1.57 g, 5.55 mmol, 5.0 eq.), bis(dibenzylacetone)palladium (192 mg, 0.33 mmol, 30%), and 2-biscyclohexylphosphine-2',6'-dimethoxybiphenyl (182 mg, 0.44 mmol, 40%) were loaded into a reaction tube. After replacing the air in the system with nitrogen using the Shrek technique, 1,2-dimethylbenzene (40 mL) and triethylamine (3 mL) were injected. The system was placed in an oil bath at 110 °C and reacted for 12 h. After the reaction was stopped, the system was concentrated and separated by column chromatography with a petroleum ether:dichloromethane polarity of 5:1 to 1:4 to give compound 5 of Formula II (431 mg, yield 62.6%).

[0102] Compound 8 of Formula III (300 mg, 0.94 mmol, 1.0 eq.), compound 10 of Formula IV (1.33 g, 4.69 mmol, 5.0 eq.), bis(dibenzylacetone)palladium (162 mg, 0.28 mmol, 30%), and 2-biscyclohexylphosphine-2',6'-dimethoxybiphenyl (154 mg, 0.37 mmol, 40%) were loaded into a reaction tube. After replacing the air in the system with nitrogen using the Shrek technique, 1,2-dimethylbenzene (40 mL) and triethylamine (3 mL) were injected. The system was placed in an oil bath at 110 °C and reacted for 12 h. After the reaction was stopped, the system was concentrated and separated by column chromatography with a petroleum ether:dichloromethane polarity of 5:1 to 1:4 to give compound 6 of Formula II (378 mg, yield 61.6%).

[0103] Compound 4 (100 mg, 0.19 mmol, 1.0 eq.) of Formula II and 2,3-dichloro-5,6-dicyanobenzoquinone (174 mg, 0.77 mmol, 4.0 eq.) were placed in a two-necked round-bottom flask. After replacing the air in the system with nitrogen using the Shrek technique, ultradry dichloromethane (50 mL) was injected, followed by slow injection of trifluoromethanesulfonic acid (0.85 mL, 9.55 mmol, 50 eq.). The system was allowed to react at room temperature for 1 h. After the reaction was stopped, 1 mL of hydrazine hydrate was slowly added dropwise to quench the reaction. Water was then added to the system to obtain the organic phase, which was concentrated and separated by column chromatography with a dichloromethane:ethyl acetate ratio of 100:1, yielding compound 1 (3.4 mg, yield 4.7%) of Formula I.

[0104] Compound 5 of Formula II (100 mg, 0.15 mmol, 1.0 eq.) and 2,3-dichloro-5,6-dicyanobenzoquinone (134 mg, 0.59 mmol, 4.0 eq.) were placed in a two-necked round-bottom flask. After replacing the air in the system with nitrogen using the Shrek technique, ultradry dichloromethane (50 mL) was injected, followed by slow injection of trifluoromethanesulfonic acid (0.65 mL, 7.5 mmol, 50 eq.). The system was allowed to react at room temperature for 1 h. After the reaction was stopped, 1 mL of hydrazine hydrate was slowly added dropwise to quench the reaction. Water was then added to the system to obtain the organic phase, which was concentrated and separated by column chromatography with a dichloromethane:ethyl acetate ratio of 25:1, yielding compound 2 of Formula I (5.7 mg, yield 7.2%).

[0105] Compound 6 of Formula II (500 mg, 0.69 mmol, 1.0 eq.) and 2,3-dichloro-5,6-dicyanobenzoquinone (623 mg, 2.75 mmol, 4.0 eq.) were placed in a two-necked round-bottom flask. After replacing the air in the system with nitrogen using the Shrek technique, 250 mL of ultradry dichloromethane was injected, followed by slow injection of trifluoromethanesulfonic acid (3.1 mL, 34.5 mmol, 50 eq.). The system was allowed to react at room temperature for 1 h. After the reaction was stopped, 1 mL of hydrazine hydrate was slowly added dropwise to quench the reaction. Water was then added to the system to obtain the organic phase, which was concentrated and separated by column chromatography with a dichloromethane:ethyl acetate ratio of 25:1, yielding compound 3 of Formula I (4.0 mg, yield 1.0%).

[0106] The structural verification data is as follows:

[0107] Compound 4:

[0108] 1 H NMR (400MHz, CDCl3): δ (ppm) 7.89-7.85 (m, 4H), 7.83 (d, J = 8.4Hz, 2H), 7.63-7.56 (m, 8H), 7.53 (d, J = 6.8Hz, 2H), 0.31 (s, 18H).

[0109] 13 C NMR (100MHz, CDCl3): δ (ppm) 152.7, 144.1, 142.2, 137.2, 136.9, 129.7, 129.4, 128.5, 128.0, 127.7, 127.6, 126.4, 125.2, 123.3, 1.5.

[0110] HRMS (MALDI-FTICR): Calculated value is C 36 H 34Si2(M + ): 522.2193, mass spectrometry peak position: 522.2195.

[0111] Compound 5 (R = TMS):

[0112] 1 H NMR (600MHz, CDCl3): δ (ppm) 8.64 (d, J = 7.8Hz, 2H), 8.26 (d, J = 7.8Hz, 2H), 7.81 (d, J = 7 .2Hz,2H),7.65(m,4H),7.59(t,J=7.8Hz,2H),7.48(s,6H),7.05(s,2H),0.27(s,18H).

[0113] 13 C NMR (100MHz, CD2Cl2): δ (ppm) 187.9, 152.6, 146.4, 144.2, 140.9, 138.5, 136.0, 13 5.2,134.2,133.1,132.1,131.8,130.4,130.0,129.8,129.0,126.9,126.5,-0.1.

[0114] HRMS (MALDI-FTICR): Calculated value is C 46 H 38 O2Si2(M + (): 678.2405, mass spectrometry peak position: 678.2413.

[0115] Compound 6 (R = TMS):

[0116] 1 H NMR (400MHz, CDCl3): δ (ppm) 8.63 (dd, J = 6.4, 3.6Hz, 2H), 8.27 (d, J = 8.0Hz, 2H), 8.00 (d, J = 8. 0Hz,2H),7.95(s,2H),7.82(d,J=7.2Hz,2H),7.64-7.55(m,10H),7.17(s,2H),0.15(s,18H).

[0117] 13 C NMR (100MHz, CDCl3): δ (ppm) 188.6, 152.9, 146.6, 144.4, 138.8, 135.5, 134. 6,134.6,133.5,133.4,132.3,130.3,129.4,129.4,129.2,127.5,126.8,0.5

[0118] HRMS (MALDI-FTICR): Calculated value is C 50 H 40 O2Si2(M + ): 728.2561, mass spectrometry peak position: 728.2561.

[0119] Compound 1:

[0120] 1 H NMR (400MHz, CDCl3): δ (ppm) 7.92 (dd, J = 8.4, 2.8Hz, 8H), 7.81 (d, J = 6.8Hz, 4H), 7.78 (d, J =6.8Hz,4H),7.66-7.59(m,8H),7.45(dd,J=8.0,2.0Hz,4H),7.12(dd,J=7.6,2.0Hz,4H).

[0121] 13 C NMR (100MHz, CDCl3): δ (ppm) 141.7, 139.6, 138.6, 135.0, 133.0, 132.1, 129.0, 128.3, 127.9, 127.9, 127.3, 127.2, 125.9, 124.3.

[0122] HRMS (MALDI-FTICR): Calculated value is C 60 H 32 (M + (): 752.2499, mass spectrometry peak position: 752.2496.

[0123] Compound 2:

[0124] 1 H NMR (400MHz, CDCl3): δ (ppm) 8.61 (dd, J=5.6, 3.6Hz, 4H), 8.31 (dd, J=7.2, 1.6Hz, 4H), 7.7 0(s,4H),7.67-7.51(m,20H),7.40(dd,J=8.0,1.6Hz,4H),7.00(dd,J=8.0Hz,1.6Hz,4H).

[0125] 13 C NMR (100MHz, CDCl3): δ (ppm) 188.9, 143.0, 141.0, 140.2, 138.9, 135.9, 135.2, 134.4, 134.3,134.2,133.7,133.5,133.4,132.6,132.2,130.6,129.1,128.4,128.2,127.1.

[0126] HRMS (MALDI-FTICR): Calculated value is C 80 H 40 O4(M + (): 1064.2921, mass spectrometry peak position: 1064.2916.

[0127] Compound 3:

[0128] 1 H NMR (400MHz, CDCl3): δ (ppm) 8.67-8.60 (m, 4H), 8.35 (d, J = 8.0Hz, 4H), 7.67-7.65 (m, 16H), 7.58 (t, J = 7.8Hz, 8H), 7.35 (s, 8H), 7.29 (s, 4H).

[0129] 13 C NMR (100MHz, CDCl3): δ (ppm) 188.7, 142.7, 142.0, 141.4, 138.6, 136.1, 135.3, 134.5, 133.8, 133.6,133.4,132.9,132.5,132.1,131.7,131.6,130.5,129.3,128.3,128.1,126.9,126.8.

[0130] HRMS (MALDI-FTICR): Calculated value is C 88 H 44 O4(M + ): 1164.3234, mass spectrometry peak position: 1164.3236.

[0131] Example 2: Crystal structures of the compounds described in Formula I (compounds 1, 2, and 3)

[0132] Preparation of crystals: Compounds 1, 2, and 3 were dissolved in organic solvents and allowed to evaporate slowly to obtain crystals.

[0133] Compounds 1, 2, and 3 exhibit different intermolecular interactions within the crystal, but they follow the same assembly pattern: molecules of the same chirality form columnar stacks, while columns of different chirality stack alternately.

[0134] Example 3: UV-Vis absorption spectra of the compounds of Formula I (compounds 1, 2, and 3) in dichloromethane solution.

[0135] The compounds described in Formula I (compounds 1, 2, and 3) were dissolved in dichloromethane solvent (concentration of 10%). -5The absorption spectra of compounds 1, 2, and 3 in solution were measured (mol / L) as follows: Figure 3 As shown. From Figure 3 It can be seen that compounds 1, 2, and 3 all exhibit multiple absorption characteristics in the range of 250–600 nm. Compound 1 shows obvious absorption peaks at 345 nm and 432 nm, while compounds 2 and 3 have similar chemical structures and absorption spectral peak shapes, with the maximum absorption wavelength tailing to 600 nm. The molar extinction coefficients of compounds 1, 2, and 3 increase sequentially.

[0136] Example 4: Circular dichroism spectrum of the compound described in Formula I (compound 2)

[0137] The racemic mixture of compound 2 (Formula I) was separated using a chiral high-performance liquid chromatography (HPLC, CHIRALPAK IC column), successfully yielding two enantiomers. The two pairs of enantiomers of compound 2 (Formula I) were dissolved in dichloromethane solvent, and the circular dichroism spectra of the two enantiomers of compound 2 were measured as follows: Figure 4 As shown. From Figure 4 It can be seen that the two components exhibit a mirror symmetry relationship between 250-600 nm and multiple positive and negative cotton effects at 252, 276, 306, 324, 354, 391, 420 and 531 nm, indicating that the two components are a pair of enantiomers.

[0138] Example 5: Synthesis of the compound described in Formula V (compound 13, R1 = 2,4,6-trimethylbenzene ring)

[0139] Chemical reaction equations such as Figure 5 As shown, the specific reaction conditions are as follows:

[0140] Compound 2 of Formula I (100 mg, 0.09 mmol, 1.0 eq.) was loaded into a reaction tube. After replacing the air in the system with nitrogen using the Shrek technique, a solution of redistilled tetrahydrofuran (25 mL) and 2,4,6-trimethylphenyl magnesium bromide in tetrahydrofuran (1 M, 3.8 mL, 3.76 mmol, 40 eq.) was injected. The system was placed in an ice bath and reacted for 4 h. After the reaction was stopped, an aqueous solution of ammonium chloride was added to quench the reaction, followed by extraction with dichloromethane and water. The organic phase was separated and the solvent was removed by rotary evaporation to give compound 11 of Formula VII (120 mg, yield 82.6%).

[0141] Compound 11 (20 mg, 0.01 mmol, 1.0 eq.) of Formula VII and stannous chloride (37 mg, 0.19 mmol, 15.0 eq.) were loaded into a reaction tube. After replacing the air in the system with nitrogen using the Shrek technique, redistilled tetrahydrofuran (8 mL) and concentrated hydrochloric acid (1 mL) were injected. The system was placed in an ice bath and reacted for 1 h. After the reaction was complete, water was added to quench the reaction, followed by extraction with dichloromethane and water to separate the organic phase. The solvent was removed by rotary evaporation, and the mixture was then purified by column chromatography using petroleum ether / dichloromethane (5:1 to 1:1) as the eluent to obtain compound 12 (25.5 mg, yield 66.9%) of Formula VI.

[0142] Compound 12 (30 mg, 0.02 mmol, 1.0 eq.) of Formula VI was loaded into a reaction tube. Then, DDQ oxidant and toluene solvent (10 mL) were injected. The system was placed in an oil bath at 90 °C and reacted for 1 h. After the reaction, the solvent was removed by rotary evaporation, and the system was then purified by column chromatography, using petroleum ether / dichloromethane (1:1 to 1:10) as the eluent to obtain compound 13 (13.5 mg, yield 13.6%) of Formula V.

[0143] The structural verification data is as follows:

[0144] Compound 11:

[0145] HRMS (MALDI-FTICR): Calculated value is C 116 H 88 O4(M + (): 1544.6677, mass spectrometry peak position: 1544.6682.

[0146] Compound 12:

[0147] 1 H NMR (700MHz, CDCl2CDCl2): δ (ppm) 7.96 (s, 4H), 7.63 (d, J = 7.7Hz, 4H), 7.26-7.20 (m, 16H), 7.13 (d, J = 7.7Hz, 4H), 7.06 (s, 4H),6.99(s,4H),6.27(d,J=10.5Hz,4H),6.14(d,J=10.5Hz,4H),4.39(s,4H),2.41(s,12H),2.18(s,12H),1.84(s,12H).

[0148] 13C NMR (175MHz, CDCl2CDCl2): δ (ppm) 142.6, 141.6, 139.1, 138.8, 137.0, 136.9, 136.8, 136.6, 135.6, 135.5, 135.4, 133. 1,132.8,132.3,131.5,131.2,130.9,130.5,130.3,130.3,129.0,128.9,128.5,126.3,125.6,42.6,21.4,20.3,20.1.

[0149] HRMS (MALDI-FTICR): Calculated value is C 116 H 84 (M + (): 1476.6568, mass spectrometry peak position: 1476.6596.

[0150] Compound 13:

[0151] HRMS (MALDI-FTICR): Calculated value is C 116 H 80 (M + (): 1472.6255, mass spectrometry peak position: 1472.6260.

[0152] Example 6: Temperature-variable 1H NMR spectrum of the compound described in Formula V (compound 13)

[0153] Compound 13 was dissolved in deuterated dichloromethane and deuterated tetrachloroethane, respectively, and its hydrogen spectroscopy was performed using a 500 MHz nuclear magnetic resonance spectrometer, both with and without temperature variations. Figure 6 As shown, the 1H NMR spectrum of compound 13 shows no obvious signal at room temperature, with broad peaks in the aromatic region, and no significant changes within the temperature range of 198K-393K. This indicates that compound 13 is a free radical species with open-shell properties and a strong spin distribution.

[0154] Example 7: Electron paramagnetic resonance spectrum of the compound described in Formula V (compound 13)

[0155] Compound 13 was dissolved in tetrachloroethane and tested using an electron paramagnetic resonance spectrometer. Figure 7 As shown, compound 13 exhibits a distinct free radical spin signal at room temperature, further demonstrating that compound 13 is a free radical compound with open-shell properties.

[0156] Example 8: Ultraviolet-visible absorption spectrum of compound V (compound 13) in toluene solution over time under ambient sunlight and air conditions.

[0157] Compound 13 was dissolved in toluene (concentration 10%).-5 The UV-Vis absorption spectrum of compound 13 in toluene solution (mol / L) was measured over time under ambient conditions of room temperature, sunlight, and air. Figure 8 As shown. From Figure 8 It was found that compound 13 exhibits significant absorption peaks at 287 nm, 418 nm, 657 nm, and 709 nm, and a triple near-infrared absorption peak at 980 nm, 1131 nm, and 1350 nm, further indicating that compound 13 is a free radical compound. With prolonged storage time, the absorbance of the UV-Vis absorption curve of compound 13 gradually decreased, indicating that compound 13 gradually decomposes and bleachs under room temperature, sunlight, and air conditions. After 29 days of continuous testing, we performed linear fitting on the absorbance at a wavelength of 418 nm to calculate the half-life t of compound 13. 1 / 2 The time was 48 days. This indicates that although compound 13 is a free radical compound, it has excellent stability and the potential to be used as a stable free radical magnetic material.

[0158] The present invention has been described in detail above. Those skilled in the art will recognize that the invention can be practiced in a wide range of ways with equivalent parameters, concentrations, and conditions without departing from its spirit and scope, and without requiring unnecessary experiments. While specific embodiments have been provided, it should be understood that further modifications can be made to the invention. In summary, according to the principles of the invention, this application is intended to include any changes, uses, or improvements to the invention, including changes made using conventional techniques known in the art that depart from the scope disclosed herein.

Claims

1. The compound shown in Formula I: In Formula I, the conjugated unit Ar is independently selected from either a substituted or unsubstituted benzene-type polycyclic aromatic hydrocarbon segment fused at the edge of a five-membered ring or a substituted or unsubstituted non-benzene-type polycyclic aromatic hydrocarbon segment fused at the edge of a five-membered ring; The benzene-type polycyclic aromatic hydrocarbon fragment is independently selected from any one of the following: benzene ring, biphenyl, fluorenyl, naphthyl ring, anthracene ring, pyrene ring, perylene ring, thiophene ring, pyridine ring, pyrrole ring, furan ring, and carbazole ring; The substituents in the substituted benzene-type polycyclic aromatic hydrocarbon fragment are substituted in any number and at any position in the benzene-type polycyclic aromatic hydrocarbon; The substituents are independently selected from any one of fluorine, chlorine, bromine, iodine, C1-C10 haloalkyl, nitro, ester, carboxyl, C1-C18 straight-chain or branched alkyl, C1-C18 straight-chain or branched alkoxy, C1-C18 straight-chain or branched alkylamino, trimethylsilyl (TMS), triisopropylsilyl (TIPS), and tert-butyldimethylsilyl (TBDMS); The non-benzene polycyclic aromatic hydrocarbon fragment is independently selected from any one of benzocycloheptenene, dibenzocycloheptenone, and dibenzocyclooctene; The bridging unit π is independently selected from either benzene-type polycyclic aromatic hydrocarbons or non-benzene-type polycyclic aromatic hydrocarbon segments.

2. The compound of claim 1, wherein In Formula I, the conjugated unit Ar is either a naphthalene ring fused at the edge of a five-membered ring or a dibenzoheptenone ring fused at the edge of a five-membered ring; the bridging unit π in Formula I is either a benzene ring or a naphthalene ring.

3. The compound of claim 1, wherein The compound shown in Formula I has the following structure:

4. A method for preparing the compound according to any one of claims 1-3, comprising the following steps: subjecting the compound of formula II to an oxidative coupling reaction in an organic solvent in the presence of an oxidizing agent and an acid to obtain the compound of formula I. The definitions of conjugate unit Ar and bridging unit π in Formula II are the same as those in claim 1. R stands for trimethylsilyl (TMS) or a hydrogen atom.

5. The method according to claim 4, characterized in that, The reaction is carried out in a nitrogen or air atmosphere; The temperature for the oxidative coupling reaction is 0-80℃; The oxidative coupling reaction takes 0.5-24 hours; The oxidant is selected from at least one of ferric chloride, lead dioxide, manganese dioxide, benzoquinone, o-tetrachlorobenzoquinone, p-tetrachlorobenzoquinone, 2,3-dichloro-5,6-dicyanobenzoquinone, 3,5-di-tert-butyl-O-catechol, and oxygen; The acid is selected from at least one of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, and methanesulfonic acid; The molar ratios of the compound, oxidant, and acid shown in Formula II are 1:1-30:10-200, respectively.

6. The compound shown in formula V: In Formula V, R1 is independently selected from any one of C1-C10 haloalkyl, cyanomethyl, C1-C10 straight-chain alkyl or branched alkyl, C2-C10 straight-chain alkenyl or branched alkenyl, C1-C10 straight-chain alkynyl or branched alkynyl and aromatic ring containing a substituent. The aromatic ring is independently selected from any one of the following: benzene ring, naphthalene ring, anthracene ring, pyrene ring, perylene ring, and carbazole ring; The substituents in the substituted aromatic ring are substituted in any number and at any position on the aromatic ring; The substituents are independently selected from any one of fluorine, chlorine, bromine, C1-C10 haloalkyl, nitro, C1-C10 straight-chain alkyl or branched alkyl, C1-C10 straight-chain or branched alkoxy, trimethylsilyl (TMS), triisopropylsilyl (TIPS) and tert-butyldimethylsilyl (TBDMS). In Equation V, the bridging unit π is independently selected from either benzene-type polycyclic aromatic hydrocarbons or non-benzene-type polycyclic aromatic hydrocarbon segments.

7. A method for preparing the compound of formula V according to claim 6, comprising the following steps: subjecting the compound of formula VI to an oxidation reaction in an organic solvent in the presence of an oxidizing agent to obtain the compound of formula V: The definition of R1 in equation VI is the same as the definition of R1 in equation V; in, The oxidant is selected from at least one of oxygen, benzoquinone, o-tetrachlorobenzoquinone, p-tetrachlorobenzoquinone, 2,3-dichloro-5,6-dicyanobenzoquinone, ferric chloride, silver nitrate, cerium ammonium nitrate, lead dioxide, manganese dioxide, 3,5-di-tert-butyl-O-catechol, copper chloride, and potassium persulfate, specifically 2,3-dichloro-5,6-dicyanobenzoquinone.

8. The method according to claim 7, characterized in that, The compound shown in Formula VI was prepared by a method comprising the following steps: 1) When the conjugated unit Ar in claim 1 is a dibenzoheptanone with a five-membered ring edge fused together, the compound shown in formula I undergoes addition under the action of the Grignard reagent shown in formula VIII to obtain the compound shown in formula VII. R1-MgBr Formula VIII The definition of R1 in Formula VII and Formula VIII is the same as the definition of R1 in Formula V of claim 6; 2) The compound shown in formula VII is reduced by stannous chloride and concentrated hydrochloric acid to obtain the compound shown in formula VI.

9. Applications of the compounds of formula I in claims 1-3 and the compounds of formula V in claim 6 in near-infrared absorption, photodetection, field-effect transistors, organic solar cells, organic light-emitting diodes, chiral optics, and nonlinear optics.

10. The application of the compound shown in Formula V of claim 6 as a photoelectric and electromagnetic functional material, specifically the application of the compound shown in Formula V as a stable free radical magnetic material.

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