A method for synthesizing a tetraphenodibenzoindeno perylene having near-infrared absorption

Abstract

The application belongs to the field of organic photoelectric material synthesis, and particularly discloses a synthesis method of a tetraphenodibenzoindeno perylene with near-infrared absorption. Based on the structure and reaction characteristics of 5,12-dichloro naphthalene, a new carbon molecule with near-infrared absorption and novel structure and physical and chemical characteristics is designed and synthesized through Suzuki-Miyaura coupling reaction, Yamamoto reaction and Scholl reaction. The raw material of the application is easy to obtain, the synthesis cost is low, and the synthesis method is simple and easy to operate. The compound A presents brown color and good stability, and has potential application prospect in the fields of organic dyes and organic semiconductors.

Description

Technical Field

[0001] This invention belongs to the field of organic functional material synthesis technology, specifically relating to a method for synthesizing tetrabenzodiindendeliquane with near-infrared absorption. Background Technology

[0002] The rational bottom-up synthesis of atomically precise graphene nanoribbons and graphene nanoparticles can be achieved by tuning the band gap through molecular size, edge structure, or the addition of appropriate heteroatoms. Among graphene nanoribbons, π-phenylene and n-peri-acene (n-PA) with abundant serrated edges are potential candidate materials for fields such as organic field-effect transistors (OFETs), organic light-emitting diodes (OLEDs), and organic spintronics. π-phenylene is a linearly chain-fused polycyclic aromatic hydrocarbon, while n-PAs are aromatic hydrocarbons with two rows of π-phenylene chains fused together. Typically, the solution synthesis of longer π-phenylene (larger than hexaphenylene) remains difficult due to their poor stability under environmental conditions. In fact, longer π-phenylene exhibits singlet biradical characteristics (open-shell) in the ground state, which can be explained by the formation of additional Clar hexaphenylene to provide additional aromatic stabilization energy. Among nPAs, 2-PA and 3-PA and their derivatives have become research targets in materials chemistry. Higher nPA (n≥4) are theoretically predicted to exhibit stronger open-shell characteristics due to their narrower band gap, making their synthesis still challenging.

[0003] Based on the above analysis, this invention uses 5,12-dichlorotetrabenzene as a raw material and obtains compound A through the Suzuki-Myiaura coupling reaction, Yamamoto reaction, and Scholl reaction. The synthetic method of this invention is simple, easy to perform, low in cost, and yields high results; therefore, this synthetic technology has great potential for widespread application. Summary of the Invention

[0004] This invention provides a simple and easy-to-implement method for synthesizing compound A through a reasonable process route and reaction conditions. This method has the advantages of simple operation and high yield. This invention uses compound S1 as a starting material, which undergoes a Suzuki-Miyaura coupling reaction with 4-tert-butylphenylboronic acid under palladium catalysis to obtain compound S2. Compound S2 undergoes a Yamamoto reaction with bis(1,5-cyclooctadiene)nickel(O) to obtain compound S3. Compound S3 then undergoes a Scholl reaction in the presence of 2,3-dichloro-5,6-dicyanobenzoquinone to obtain the target compound A. The reaction equations are as follows:

[0005] The specific operating steps are as follows: Step 1: A certain amount of compound S1, 4-tert-butylphenylboronic acid, tetrakis(triphenylphosphine)palladium, and potassium carbonate are added to a Schlenk reaction tube and dissolved in a mixed solvent of toluene and water at a volume ratio of 10:1 under a nitrogen atmosphere. The reaction mixture is stirred at a certain temperature for a certain time. After the reaction is completed, the reaction mixture is cooled to room temperature, extracted three times with dichloromethane, and the organic phases are combined. The organic phase is washed with saturated brine, and the organic phase is separated. The organic phase is dried with anhydrous sodium sulfate for a certain time, filtered, and the solvent is recovered by vacuum distillation. The residue is separated by silica gel column chromatography using n-hexane as the eluent. The second yellow fluorescent band is collected to obtain a solution of compound S2. The solvent is recovered by vacuum distillation, and the residue is dried under vacuum to obtain an orange-yellow solid, which is compound S2.

[0006] Step 2: A certain amount of bis(1,5-cyclooctadiene)nickel (0), 2,2′-bipyridine, and 1,5-cyclooctadiene were added to a Schlenk reaction tube and dissolved in toluene under a nitrogen atmosphere. The above solution was stirred and reacted for a certain time at a certain temperature under light-protected conditions. Then, a toluene solution of compound S2 was added. The reaction mixture was stirred and reacted for a certain time at a certain temperature. After the reaction was completed, it was cooled to room temperature, and the reaction solution was extracted with dichloromethane. The organic phases were combined, washed with saturated brine, and separated. The organic phase was dried with anhydrous sodium sulfate for a certain time, filtered, and the solvent was recovered by vacuum distillation. The residue was separated by silica gel column chromatography using a 1:6 volume ratio mixture of dichloromethane and n-hexane as the eluent. The third yellow fluorescent eluent band was collected to obtain a solution of compound S3. The solvent was recovered by vacuum distillation, and the residue was dried under vacuum to obtain an orange-yellow solid, which was compound S3.

[0007] Step 3: According to a certain molar ratio, compound S3 and 2,3-dichloro-5,6-dicyanobenzoquinone were dissolved in a certain amount of anhydrous dichloromethane under a nitrogen atmosphere. A certain amount of trifluoromethanesulfonic acid was added, and the reaction was stirred at a certain temperature for a certain time. After the reaction was completed, a certain amount of hydrazine hydrate was added to the reaction flask under ice-water bath cooling, and the reaction was stirred for a certain time. The reaction mixture was extracted with dichloromethane, and the organic phases were combined. The organic phase was washed with saturated brine to separate the organic phase. The organic phase was dried with anhydrous sodium sulfate, filtered, and the solvent was recovered by vacuum distillation. The residue was separated by silica gel column chromatography. A solution of compound A was obtained by eluent with a mixed solvent of carbon disulfide and n-hexane in a volume ratio of 1:1. The solvent was recovered by vacuum distillation, and the brown solid obtained after vacuum drying was compound A. Attached Figure Description

[0008] Figure 1 This is the 1H NMR spectrum of compound S1.

[0009] Figure 2This is the carbon NMR spectrum of compound S1.

[0010] Figure 3 This is the 1H NMR spectrum of compound S2.

[0011] Figure 4 This is the carbon NMR spectrum of compound S2.

[0012] Figure 5 This is the 1H NMR spectrum of compound S3.

[0013] Figure 6 This is the carbon NMR spectrum of compound S3.

[0014] Figure 7 This is the 1H NMR spectrum of compound A.

[0015] Figure 8 This is the single-crystal structure diagram of compound A.

[0016] Figure 9 These are the absorption spectra of compounds S3 and A in the ultraviolet-visible region.

[0017] Figure 10 This is the photostability spectrum of compound A.

[0018] Figure 11 These are cyclic voltammetry diagrams for compounds S3 and A. Implementation

[0019] Example 1. Synthesis of compound S2

[0020] The raw material 5,12-dichlorotetrabenzene (S1) used in the embodiments of the present invention was synthesized by referring to the method of application number 2023116597929.

[0021] The NMR spectrum of compound S1 was measured using a Bruker AVANCE NEO NMR spectrometer, and the specific data are as follows: 1 H NMR (600 MHz, CDCl3) δ 9.18 (s, 2H), 8.55–8.50 (m, 2H), 8.11–8.07 (m, 2H), 7.59–7.54 (m, 2H), 7.52–7.48 (m, 2H). 13 C NMR (151 MHz, CDCl3) δ 192.57, 132.20, 128.49, 128.06, 127.51, 126.74, 126.50, 125.16, 124.31.

[0022] 200 mg (0.68 mmol) of 5,12-dichlorotetraphenyl (S1), 133 mg (0.75 mmol) of 4-tert-butylphenylboronic acid, 16 mg (0.014 mmol) of tetrakis(triphenylphosphine)palladium, and 187 mg (1.36 mmol) of potassium carbonate were added to a 100 mL Schlenk reaction tube. After purging with nitrogen three times, 8 mL of toluene and 0.8 mL of distilled water were added under a nitrogen atmosphere. The solution was heated to 95 °C and stirred at this temperature for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, and the reaction mixture was extracted three times with 20 mL of dichloromethane each time. The organic phases were combined and washed with an equal volume of saturated brine. The organic phase was then separated, dried over anhydrous sodium sulfate for 2 hours, filtered, and the filtrate was distilled under reduced pressure to recover the solvent, yielding a dark yellow solid, which was the crude product. The crude product was separated by silica gel column chromatography with a mesh size of 200-300. Hexane was used as the eluent. The eluent of the second yellow fluorescent band was collected to obtain a solution of compound S2. The solvent was recovered by vacuum distillation and dried under vacuum to obtain 184 mg of orange-yellow solid, which was compound S2, with a yield of 69%.

[0023] The NMR spectrum of compound S2 was measured using a Bruker AVANCE NEO NMR spectrometer. Specific data are as follows: 1 H NMR (600 MHz, CDCl3): δ 9.22 (s, 1H), 8.56 (d, 1H), 8.35 (s, 1H), 8.09(d, J = 8.6 Hz, 1H), 7.84 (d, J = 8.6 Hz, 1H), 7.69 (d, J = 8.9 Hz, 1H), 7.65(d, J = 8.9 Hz, 2H), 7.54–7.50 (m, 1H), 7.46–7.38 (m, 3H), 7.38–7.33 (m, 1H), 7.32–7.28 (m, 1H), 1.51 (s, 9H); 13 C NMR (151 MHz, CDCl3) δ 150.90, 137.28, 135.57, 132.09, 131.47, 131.26, 130.33, 130.03, 128.69, 128.64, 128.36, 127.72, 127.45, 126.77, 126.55, 126.12, 125.65, 125.54, 125.08, 124.93, 123.70, 34.99, 31.72.

[0024] Example 2. Synthesis of compound S3

[0025] 48 mg (0.30 mmol) of 2,2′-bipyridine, 84 mg (0.30 mmol) of bis(1,5-cyclooctadiene)nickel(0), and 0.04 mL (0.30 mmol) of cyclooctadiene were added to a 25 mL Schlenk reaction tube and dissolved in 2 mL of toluene under a nitrogen atmosphere. The resulting deep purple solution was stirred at 60 °C for 30 min in the dark. Then, 100 mg (0.25 mmol) of compound S2 dissolved in 10 mL of toluene was added. The reaction mixture was stirred at 110 °C for 24 h. After the reaction was complete, the reaction mixture was extracted three times with 10 mL of dichloromethane each time. The organic phases were combined and washed with an equal volume of saturated brine. The organic phase was separated, dried over anhydrous sodium sulfate for 2 h, filtered, and the filtrate was distilled under reduced pressure to recover the solvent, yielding a dark yellow solid, which was the crude product. The crude product was separated by silica gel column chromatography with a 200-300 mesh. A mixed solvent of dichloromethane and n-hexane with a volume ratio of 1:6 was used as the eluent. The third yellow fluorescent band was collected to obtain a solution of compound S3. The solvent was recovered by vacuum distillation, and the product was dried under vacuum to obtain 50 mg of orange-yellow solid, which was compound S3, with a yield of 55%.

[0026] The NMR spectrum of compound S3 was measured using a Bruker AVANCE NEO NMR spectrometer. Specific data are as follows: 1 H NMR (600 MHz, CD2Cl2) δ 8.54 (s, 2H), 7.90 (s, 2H), 7.86 (d, J = 9.0 Hz,2H), 7.84 – 7.78 (m, 6H), 7.73 (d, J = 7.7, 1.9 Hz, 2H), 7.66 (d, J = 7.7,1.9 Hz, 2H), 7.45 (d, J = 8.7 Hz, 2H), 7.28 – 7.23 (m, 4H), 7.17 – 7.14 (m,4H), 7.08 – 7.04 (m, 2H), 1.63 (s, 18H); 13 C NMR (151 MHz, CDCl3) δ150.71, 138.33, 136.32, 133.75, 131.52, 131.48, 131.45, 131.32, 130.61, 129.96, 129.77, 128.61, 127.65, 127.36, 126.46, 126.04, 125.62, 125.60, 125.43, 125.18, 125.14, 124.97, 35.05, 31.81.

[0027] Example 3. Synthesis of Compound A

[0028] 34 mg (0.05 mmol) of compound S3 and 51 mg (0.23 mmol) of 2,3-dichloro-5,6-dicyanobenzoquinone were added to a 50 mL two-necked flask. After purging with nitrogen three times, 20 mL of anhydrous dichloromethane was added, and the mixture was stirred until the reactants were completely dissolved. 1 mL of trifluoromethanesulfonic acid was added, and the mixture was stirred at 25 °C for 2 hours. Under stirring and cooling in an ice-water bath, 0.5 mL of hydrazine hydrate was added dropwise, and the mixture was stirred for 10 min. 10 mL of water was added, and the mixture was stirred thoroughly. The mixture was extracted three times, with 10 mL of dichloromethane added each time. The organic phases were combined and washed once with an equal volume of saturated brine. The organic phase was separated and dried over anhydrous sodium sulfate for 2 hours. After filtration, the solvent was recovered by vacuum distillation to obtain a brown solid. The solid was separated by silica gel column chromatography at a volume ratio of 1:1. A solution of compound A was obtained by eluenting with a mixture of carbon disulfide and n-hexane. The first yellow band was collected. The solvent was recovered by vacuum distillation. The residue was dried under vacuum to obtain 16 mg of brown solid, which was compound A, with a yield of 45%.

[0029] The NMR spectrum of compound A was measured using a Bruker AVANCE NEO NMR spectrometer. Specific data are as follows: 1 H NMR (600 MHz, CD2Cl2) δ 8.68 (dd, J = 31.8, 8.7 Hz, 4H), 8.27 (s, 2H), 8.17 – 8.06 (m, 6H), 7.65 – 7.56 (m, 4H), 7.37 (d, J = 7.9 Hz, 2H), 7.33 –7.26 (m, 4H), 1.60 (s, 18H).

[0030] The single-crystal structure of compound A was determined at 100 K using a Bruker Single Crystal CCD X-ray Diffractometer (SMART APEX II). The crystal data are as follows: C 56 H 40 ;crystal size 0.15 × 0.1 ×0.08 mm 3 , triclinic, P-1 (no. 2), a = 12.3364(5) Å, b = 12.4878(6) Å, c =14.9558(7) Å, α = 73.904(4)°, β = 77.296(4)°, γ = 74.882(4)°, V = 2122.21(18)Å 3 , Z = 2 Completeness 99.6%, R1 = 0.0865, w R2 = 0.2344 (I > 2σ(I)), GOF =1.003.

Claims

1. A method for synthesizing a tetrabenzodiindene perylene compound A with near-infrared absorption, characterized in that: The synthetic route for compound A is as follows:

2. The method for synthesizing tetrabenzodiindene perylene compound A with near-infrared absorption according to claim 1, characterized in that, The molar ratio of the reactants for the synthesis of compound S2 is: compound S1: 4-tert-butylphenylboronic acid: tetrakis(triphenylphosphine)palladium: potassium carbonate = 1:1.1:0.02:

2.

3. The method for synthesizing tetrabenzodiindene perylene compound A with near-infrared absorption according to claim 1, characterized in that, The reaction conditions for synthesizing compound S2 were: a reaction temperature of 95℃ and a reaction time of 12 hours.

4. The method for synthesizing tetrabenzodiindene perylene compound A with near-infrared absorption according to claim 1, characterized in that, The method for synthesizing compound S2 involves separating compound S2 using silica gel column chromatography with a mesh size of 200-300, and the eluent being n-hexane.

5. The method for synthesizing tetrabenzodiindene perylene compound A with near-infrared absorption according to claim 1, characterized in that, The molar ratio of the reactants for the synthesis of compound S3 is: compound S2: bis(1,5-cyclooctadiene)nickel(0): 2,2′-bipyridine: cyclooctadiene = 1:1.2:1.2:1.

2.

6. The method for synthesizing tetrabenzodiindene perylene compound A with near-infrared absorption according to claim 1, characterized in that, The reaction conditions for synthesizing compound S3 were as follows: the reaction temperature for the first stage was 60℃ and the reaction time was 30 minutes; the reaction temperature for the second stage was 110℃ and the reaction time was 24 hours.

7. The method for synthesizing tetrabenzodiindene perylene compound A with near-infrared absorption according to claim 1, characterized in that, The method for synthesizing compound S3 involves separating compound S3 using silica gel column chromatography with a 200-300 mesh, and using a mixture of dichloromethane and n-hexane in a volume ratio of 1:6 as the eluent.

8. The method for synthesizing tetrabenzodiindene perylene compound A with near-infrared absorption according to claim 1, characterized in that, The molar ratio of the reactants for the synthesis of compound A is: compound S3: 2,3-dichloro-5,6-dicyanobenzoquinone = 1:4.

5.

9. The method for synthesizing tetrabenzodiindene perylene compound A with near-infrared absorption according to claim 1, characterized in that, The reaction conditions for synthesizing compound A are: reaction temperature of 25℃ and reaction time of 2 hours.

10. The method for synthesizing tetrabenzodiindene perylene compound A with near-infrared absorption according to claim 1, characterized in that, The method for synthesizing compound A involves separating compound A using silica gel column chromatography with a 200-300 mesh mesh, and using a 1:1 volume ratio of carbon disulfide and n-hexane as the eluent.

11. The method for synthesizing tetrabenzodiindene perylene compound A with near-infrared absorption according to claim 1, characterized in that, Compound A appears brown under natural light, and its maximum absorption wavelength is in the near-infrared region.

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