Conjugated fused macrocyclic materials containing cyclobutadiene and methods of making and using the same

Abstract

This invention belongs to the field of organic optoelectronic materials technology, specifically a class of conjugated fused macrocyclic materials containing a cyclobutadiene structure, their preparation method, and applications. The structure of this type of material is shown in formulas 1) and 2), where R1 is C1-C2. 30 Alkoxy, C1-C 30 alkoxy-substituted phenyl or phenyl; R2 is C1-C 30 alkyl group, C1-C 30 The alkyl group replaces the phenyl group or the phenyl group. The raw materials used in this invention are simple in structure, inexpensive, readily available, and easy to purify, offering advantages such as low cost and ease of preparation. Furthermore, the anti-aromatic properties of cyclobutadiene endow this type of conjugated fused macrocyclic material with a unique electronic structure and nanoporous structure. The fluorescence quantum yield of this class of conjugated fused macrocyclic materials exceeds 54%, currently ranking among the top levels for pure hydrocarbon conjugated fused macrocyclic materials. Further testing revealed that the carrier mobility of its thin-film organic field-effect transistor is ~×10⁻⁶. ‑4 cm 2 V ‑1 s ‑1 .

Description

Technical Field

[0001] This invention belongs to the field of organic optoelectronic materials technology, specifically relating to a class of conjugated fused macrocyclic materials containing cyclobutadiene, their preparation methods, and applications. Background Technology

[0002] As one of the most widely used active devices in microelectronics, the field-effect transistor (FET) has become a strong competitor to the bipolar transistor (BPT) and a crucial component in the microelectronics industry due to its advantages such as low input power consumption, low noise, wide safe operating area, high impedance, and absence of secondary breakdown. Since its inception, the materials used in its fabrication have primarily been silicon, germanium, and other inorganic semiconductor materials. However, inorganic FETs suffer from drawbacks such as high manufacturing costs, difficulty in single-crystal fabrication, the need for high-temperature processes, the requirement for rigid substrates, and difficulty in achieving large surface areas. Furthermore, inorganic FETs are approaching the natural limits of miniaturization. In contrast, organic semiconductor materials offer advantages such as low production costs, wide availability, simpler processes, no need for high temperatures, and the ability to use flexible substrates.

[0003] Traditional high-mobility organic semiconductor materials are mostly linear fused small molecules or polymer conjugated systems linked by single bonds. Fully fused conjugated macrocycles (such as macrocyclic graphene fragments and carbon nanoribbons) are a new type of organic optoelectronic semiconductor materials. Due to their unique electronic and spatial geometric characteristics, they are expected to achieve breakthrough applications in organic optoelectronic devices and high-mobility luminescent supramolecular materials. The main challenges are the difficulty in accurately synthesizing fully fused conjugated macrocycles using wet chemical methods, poor molecular planarity, and insufficient exploration of optoelectronic functions. Kekulene (Benzenoid versus Annulenoid Aromaticity: Synthesis and Properties of Kekulene, Angew. Chem. Int. Ed., 1978, 17, 372) and its homologue Octulene (A Hyperbolic Molecular Belt that Binds Chloride Anions, Angew. Chem. Int. Ed., 2016, 55, 14072), as well as carbon nanobelts (Science, 2017, 356, 172), have all been successfully synthesized, effectively promoting the development of fully fused conjugated macrocyclic structures. Currently, most of these fully fused conjugated macrocyclic structures use a six-membered benzene ring as the basic building block, satisfying the (4n+2) Hückel rule, and are conjugated aromatic systems. Summary of the Invention

[0004] The purpose of this invention is to provide a class of conjugated fused macrocyclic materials containing cyclobutadiene, their preparation methods, and applications. The anti-aromatic properties of cyclobutadiene in the conjugated fused macrocyclic materials of this invention endow them with unique electronic and nanoporous structures, making them excellent raw materials for organic optoelectronic materials. Introducing the cyclobutadiene structure into the macrocyclic material can regulate the topology and aromaticity of the conjugated fused macrocycle. The fluorescence quantum yield of this class of conjugated fused macrocyclic materials exceeds 54%, currently ranking among the top levels for pure hydrocarbon conjugated fused macrocyclic materials. Further testing shows that the carrier mobility of its thin-film organic field-effect transistor is ~×10⁻⁶. -4 cm 2 V -1 s -1 In addition, macrocyclic materials have the advantages of inexpensive and readily available raw materials, low cost, ease of preparation, and ease of purification.

[0005] This invention provides a class of conjugated fused macrocyclic materials containing cyclobutadiene, the general structural formula of which is shown in Formula 1) or Formula 2):

[0006]

[0007] In the formula, R1 is C1-C 30 Alkoxy, C1-C 30 alkoxy-substituted phenyl or phenyl; R2 is C1-C 30 alkane group, C1-C 30 Alkyl groups can replace phenyl or phenyl groups.

[0008] Preferably, R1 is C5-C 25 Alkoxy, C5-C 25 alkoxy-substituted phenyl or phenyl; R2 is C5-C 25 Alkyl group, C5-C 25 Alkyl-substituted phenyl or phenyl

[0009] More preferably, R1 and R2 are independently selected from one of the chemical groups shown in formulas 3)-5):

[0010]

[0011] In the formula, R3, R4, and R5 are independent and represented by C1-C. 10 alkane group or C1-C 10 Alkyl group.

[0012] This invention also provides a method for preparing the above-mentioned cyclobutadiene-containing compound, comprising the following steps: first, using compound A and compound B1 or B2 as starting materials, a Suzuki coupling reaction is performed to obtain the corresponding product C1 or C2; then, compound C1 or C2 and methylmethoxytriphenylphosphine chloride undergo a Wittig reaction under alkaline conditions to generate product D1 or D2; finally, compound D1 or D2 undergoes a Friedel-Crafts reaction under the action of a catalyst to obtain a conjugated fused macrocyclic material containing cyclobutadiene as shown in formula 1) or formula 2), the synthetic route of which is as follows:

[0013]

[0014]

[0015] In the formula, R1 is C1-C 30 Alkoxy, C1-C 30 alkoxy-substituted phenyl or phenyl; R2 is C1-C 30 alkane group, C1-C 30 Alkyl groups can replace phenyl or phenyl groups.

[0016] In this invention, the Suzuki coupling reaction conditions are as follows: In a solvent, in the presence of a base, a catalyst, and a ligand, compound A is subjected to a Suzuki coupling reaction with compound B1 or B2 to obtain the corresponding product C1 or C2. Preferably, the solvent is one or more of water, benzene, toluene, xylene, decahydronaphthalene, diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-pentyl ether, dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,1-diethoxymethane, chloroform, 1,2-dichloroethane, and anisole; the base is one or more of sodium tert-butoxide (t-BuONa), potassium tert-butoxide (t-BuOK), potassium carbonate (K2CO3), sodium carbonate (Na2CO3), and potassium phosphate (K3PO4). The catalysts are tetra(triphenylphosphine)palladium (Pd(PPh3)4), bis(dibenzylacetone)palladium (Pd(dba)2), tri(dibenzylacetone)dipalladium chloroform (Pd2(dba)3·CHCl3), tri(dibenzylacetone)dipalladium (Pd2(dba)3), palladium acetate (Pd(OAc)2), palladium dichloride (PdCl2), and chloro(2-dicyclohexylphosphino-2′,4′,6′-triisopropyl-1,1′-biphenyl)[2-(2′-amino-1,1′-biphenyl)]palladium(II) (XPhos One or more of Pd G2); the ligand is one or more of triphenylphosphine (PPh3), tri-tert-butylphosphine (P(t-Bu)3), tri-tert-butylphosphine tetrafluoroborate, 2,2′-bis(diphenylphosphine)-1,1′-binaphthyl (BINAP), 2-biscyclohexylphosphine-2',6'-dimethoxybiphenyl (SPhos), 2-dicyclohexylphosphine-2,4,6-triisopropylbiphenyl (Xphos), 1,2,3,4,5-pentanylphenyl-1'-(di-tert-butylphospho)ferrocene (Qphos), 2-dicyclohexylphosphine-2'-methylbiphenyl (MePhos), 2-(di-tert-butylphosphine)biphenyl (JohnPhos), and 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene (XantPhos);

[0017] The volume-to-molar ratio of the solvent to compound A is 2:1 to 50:1 mL / mmol; the molar ratio of compound A to compound B is 0.1:1 to 4.0:1; the reaction temperature is 25℃ to 100℃, and the reaction time is 6h to 48h.

[0018] In this invention, the Wittig reaction conditions are as follows: the reaction is carried out under ice bath conditions, the base is potassium tert-butoxide, the reaction solvent is tetrahydrofuran, and the reaction time is 1-3 hours.

[0019] In this invention, the Friedel-Crafts reaction conditions are as follows: the reaction is carried out at room temperature, the catalyst is bismuth trifluoromethanesulfonate (Bi(OTf)3), the reaction solvent is 1,2-dichloroethane, and the reaction time is 1-3 h.

[0020] Furthermore, the present invention also provides the application of conjugated fused macrocyclic materials containing cyclobutadiene, as shown in Formula E, in organic field-effect transistor devices.

[0021] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0022] 1) Traditional high-mobility luminescent materials are mostly fused-ring aromatic hydrocarbons or chain-like conjugated systems linked by single bonds. Fully fused conjugated macrocycles (such as macrocyclic graphene fragments and carbon nanoribbons) are a novel class of organic optoelectronic semiconductor materials, and due to their unique electronic and spatial geometric characteristics, they hold promise for breakthrough applications in organic optoelectronic devices and high-mobility luminescent supramolecular materials. The main challenges are the difficulty in accurately synthesizing fully fused conjugated macrocycles using wet chemical methods and the lack of exploration into their optoelectronic functions (Adv. Funct. Mater. 2023, 33, 2305249). This invention provides a simple and effective method for accurately synthesizing fully fused conjugated macrocycles containing cyclobutadiene, and can effectively adjust the spatial geometry of the fully fused conjugated macrocycles to obtain conjugated fused macrocycles with pure hydrocarbon structures.

[0023] 2) Currently, most of these fully fused conjugated macrocyclic structures use a six-membered benzene ring as the basic building block, satisfying the (4n+2) Hückel rule, and are conjugated aromatic systems. However, cyclobutadiene does not satisfy the Hückel rule. This invention introduces an anti-aromatic four-membered cyclobutadiene ring into the fully fused conjugated macrocyclic structure, a process not yet reported. Furthermore, molecular structure optimization reveals that the four-membered cyclobutadiene ring can modulate the spatial topology of the fully fused conjugated macrocyclic structure (planar molecules, such as E1; or bowl-shaped molecules, such as E2), enhancing intermolecular π-π interactions and improving carrier mobility, thereby enabling multiple modulation and optimization of the performance of light-emitting field-effect transistors.

[0024] 3) This invention is based on the concept of molecular aromaticity regulation. It designs and develops novel fully fused conjugated macrocycles by introducing a four-membered ring building block containing anti-aromatic cyclobutadiene and a strategy of macrocyclic conjugation, aiming to obtain semiconductor materials with both high mobility and strong fluorescence, as well as high-performance OFET devices. The fluorescence quantum yield of the E1 material obtained in this invention is 54.04%, which is currently among the highest levels for pure hydrocarbon conjugated fused macrocycle materials. Further testing showed that the carrier mobility of its thin-film organic field-effect transistor is ~×10⁻¹⁰. -4 cm 2 V -1 s -1This provides theoretical and experimental support for the design, development, and application of other high-mobility luminescent materials. Attached Figure Description

[0025] Figure 1 : The 1H NMR spectrum of compound E1.

[0026] Figure 2 : Single crystal structure of compound E1.

[0027] Figure 3 : UV and fluorescence spectra of compound E1.

[0028] Figure 4 Optimized structural diagram of compound E2 (alkyl chain simplified to methyl).

[0029] Figure 5 : Structure diagram of E1 compound OFET device. Detailed Implementation

[0030] The present invention is further illustrated below by way of embodiments, but the invention is not limited to the scope of the embodiments described herein. Experimental methods in the following embodiments that do not specify specific conditions were performed according to conventional methods and conditions, or as selected according to the product instructions.

[0031] Example 1: Preparation of compound E1

[0032]

[0033] (1) Weigh compound A (150 mg, 0.37 mmol), compound B1 (280 mg, 0.42 mmol), and XPhos Pd G2 (50 mg, 0.06 mmol), dissolve them in 200 mL of THF, and under nitrogen protection, add 50 mL of potassium phosphate solution (0.6 M). React at 50 °C for 24 h. Remove THF from the reaction system by vacuum distillation, remove the catalyst by silica gel column chromatography, and then separate the yellow product C1 (30 mg, yield 11%) by HPLC.

[0034] (2) Weigh 89 mg (0.26 mmol) of methyl methoxytriphenylphosphine chloride and inject it into 30 mL of dry THF. Place the solution in an ice bath and inject 0.26 mL of t-BuOK (1 M in THF) under nitrogen protection. Stir for 30 minutes. Weigh product C1 (30 mg (0.020 mmol) and dissolve it in 20 mL of THF. Inject the solution into the solution. Then transfer the reaction system to room temperature and continue the reaction for 2 hours. After removing the solvent by vacuum distillation, the product D1 (30 mg, 95% yield) can be obtained by silica gel column chromatography.

[0035] (3) Add product D1 (30 mg, 0.019 mmol) and Bi(OTf)3 (25 mg, 0.038 mmol) to the reaction flask, purge the gas, and then add 30 mL of 1,2-dichloroethane. React at room temperature for 2 h. After removing the solvent by vacuum distillation, purify the product by silica gel column chromatography to obtain a bright yellow solid E1 (25 mg, 90% yield).

[0036] Figure 1 The 1H NMR spectrum of compound E1; Figure 2 This is the single-crystal structure of compound E1. Figure 3 The UV and fluorescence spectra of compound E1 are shown. The fluorescence quantum yield of material E1 obtained in this invention is 54.04%, which is among the top levels in pure carbon-hydrogen conjugated fused macrocyclic materials.

[0037] Example 2: Preparation of compound E2

[0038]

[0039] (1) Weigh compound A (170 mg, 0.42 mmol), compound B2 (260 mg, 0.42 mmol), and XPhos Pd G2 (50 mg, 0.06 mmol), dissolve them in 200 mL of THF, and under nitrogen protection, add 100 mL of potassium phosphate solution (0.6 M). React at 50 °C for 24 h. Remove THF from the reaction system by vacuum distillation, remove the catalyst by silica gel column chromatography, and then separate by HPLC to obtain the yellow product C2 (40 mg, yield 15%).

[0040] (2) Weigh 89 mg (0.26 mmol) of methylmethoxytriphenylphosphine chloride and inject it into 30 mL of dry THF. Place the solution in an ice bath and inject 0.26 mL of t-BuOK (1 M in THF) under nitrogen protection. Stir for 30 minutes. Weigh product C2 (40 mg (0.033 mmol) and dissolve it in 20 mL of THF. Inject the solution into the solution. Then transfer the reaction system to room temperature and continue the reaction for 2 hours. After removing the solvent by vacuum distillation, the product D2 (37 mg, yield 85%) can be obtained by silica gel column chromatography.

[0041] (3) Add product D2 (37 mg, 0.028 mmol) and Bi(OTf)3 (25 mg, 0.038 mmol) to the reaction flask. After purging, add 30 mL of 1,2-dichloroethane and react at room temperature for 2 hours. After removing the solvent by vacuum distillation, purify by silica gel column chromatography to obtain a bright yellow solid E2 (30 mg, 90% yield).

[0042] Figure 4 This is the optimized structural diagram of compound E2.

[0043] Application performance testing

[0044] Figure 5 To test the device structure of a thin-film transistor made of the conjugated fully fused macrocyclic material E1, a bottom-gate top-contact device structure was adopted. A gate layer, an insulating layer, an E1 organic semiconductor layer, and source and drain electrode layers were sequentially deposited on the substrate. Further testing showed that the carrier mobility of this thin-film organic field-effect transistor was ~×10⁻⁶. -4 cm 2 V -1 s -1 .

Claims

1. A class of conjugated fused macrocyclic materials containing cyclobutadiene, characterized in that, Its general structural formula is shown in Formula 1): ； Formula 1) In the formula, R1 is .

2. A method for preparing a conjugated fused macrocyclic material containing cyclobutadiene as described in claim 1, characterized in that, The process includes the following steps: First, in a solvent, in the presence of a base, a catalyst, and a ligand, compound A and compound B1 undergo a Suzuki coupling reaction to obtain the corresponding compound C1; then, compound C1 and methylmethoxytriphenylphosphine chloride undergo a Wittig reaction under the action of a base to generate product D1; finally, compound D1 undergoes a Friedel-Crafts reaction under the action of a catalyst to obtain the conjugated fused macrocyclic material containing cyclobutadiene as shown in Formula 1). The synthetic route is as follows: 。 3. The method for preparing the conjugated fused macrocyclic material containing cyclobutadiene as described in claim 2, characterized in that, The solvent is selected from one or more of water, benzene, toluene, xylene, decahydronaphthalene, diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-pentyl ether, dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,1-diethoxymethane, chloroform, 1,2-dichloroethane, or anisole; The alkali is selected from one or more of sodium tert-butoxide, potassium tert-butoxide, potassium carbonate, sodium carbonate, or potassium phosphate; The catalyst is selected from one or more of tetra(triphenylphosphine)palladium, bis(dibenzylideneacetone)palladium, tri(dibenzylideneacetone)dipalladium chloroform, tri(dibenzylideneacetone)dipalladium, palladium acetate, palladium dichloride, or chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II); The ligand is selected from one or more of triphenylphosphine, tri-tert-butylphosphine, tri-tert-butylphosphine tetrafluoroborate, 2,2′-bis(diphenylphosphine)-1,1′-binaphthyl, 2-biscyclohexylphosphine-2',6'-dimethoxybiphenyl, 2-dicyclohexylphosphine-2,4,6-triisopropylbiphenyl, 1,2,3,4,5-pentanylphenyl-1'-(di-tert-butylphospho)ferrocene, 2-dicyclohexylphosphine-2'-methylbiphenyl, 2-(di-tert-butylphosphine)biphenyl, or 4,5-bisdiphenylphosphine-9,9-dimethyloxane.

4. The method for preparing the conjugated fused macrocyclic material containing cyclobutadiene as described in claim 2, characterized in that, The volume-to-molar ratio of the solvent to compound A is 2:1 to 50:1 mL / mmol; the molar ratio of compound A to compound B1 is 0.1:1 to 4.0:1; the reaction temperature is 25℃ to 100℃, and the reaction time is 6-48h.

5. The method for preparing the conjugated fused-ring macrocyclic material containing cyclobutadiene as described in claim 2, characterized in that, The Wittig reaction conditions are as follows: the reaction is carried out in an ice bath, the base is potassium tert-butoxide, the reaction solvent is tetrahydrofuran, and the reaction time is 1-3 hours.

6. The method for preparing the conjugated fused-ring macrocyclic material containing cyclobutadiene as described in claim 2, characterized in that, The Friedel-Crafts reaction conditions are as follows: reaction at room temperature, with bismuth trifluoromethanesulfonate as the catalyst, 1,2-dichloroethane as the solvent, and a reaction time of 1-3 h.

7. The application of a conjugated fused macrocyclic material containing cyclobutadiene as described in claim 1 in an organic field-effect transistor.

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