Benzene ring connected anthraquinone-tetracene dimer and preparation method thereof

Abstract

The invention discloses a benzene ring connected anthraquinone-tetracene dimer and a preparation method thereof. The preparation method comprises the following steps: firstly, preparing tetracene borate; secondly, carrying out Suzuki reaction on the tetraphenyl borate and tribromobenzene in the presence of a palladium catalyst and potassium carbonate to obtain monobrominated tetraphenyl dimer, and carrying out Suzuki reaction on the monobrominated tetraphenyl dimer and 2-boronic acid pinacol anthraquinone in the presence of a palladium catalyst and potassium carbonate to obtain a single benzene ring connected anthraquinone-tetraphenyl dimer; and reacting the monobrominated tetraphenyl dimer with biphenyl anthraquinone borate to prepare the anthraquinone-tetraphenyl dimer connected with double benzene rings. The preparation method has the beneficial effects that the electronic coupling effect between the tetracene dimer structural unit and anthraquinone can be regulated and controlled by changing the distance between the structural units; in addition, the benzene ring connected anthraquinone-tetracene dimer provided by the invention has high electron transfer efficiency, and has potential application prospects in the aspect of improving the photoelectric conversion efficiency in photovoltaic cells.

Description

Technical Field

[0001] The invention belongs to the technical field of chemistry and relates to a type of anthraquinone-tetracene dimer connected by benzene rings and a preparation method thereof. Background Art

[0002] Acene compounds have the advantages of tunable photoelectronic properties, high charge carrier mobility and high dielectric constant, and highly efficient singlet fission has been observed in compounds such as tetracene, which can be widely used in the fields of photochemistry and photophysics. In anthraquinone-tetracene dimers, highly efficient singlet fission occurs by synthesizing dimers, thereby improving the efficiency of capturing triplet states. Therefore, the design and development of tetracene dimers that are more conducive to capturing free triplets has important research and application value. Summary of the invention

[0003] The object of the present invention is to provide a type of anthraquinone-tetracene dimer connected by benzene rings and a preparation method thereof, wherein the chemical structural formulas thereof are shown in formula (i), (ii), (iii) and (iv):

[0004]

[0005] The beneficial effect of the present invention is to improve the coupling effect between chromophores by synthesizing dimers, thereby improving the efficiency of singlet fission; in addition, a type of anthraquinone-tetraphenylene dimer of the present invention can undergo efficient singlet fission, and has potential application prospects in improving the photoelectric conversion efficiency in photovoltaic cells.

[0006] The technical solution adopted by the present invention is carried out according to the following steps:

[0007]

[0008] a. The compound of formula (1) is mixed with pinacol diboron, palladium catalyst and potassium carbonate in a Shrek tube, evacuated and then circulated with nitrogen three times, a certain proportion of organic solvent and water are added, and the reaction is carried out at 70°C for 6h. The compound of formula (i) is obtained by post-reaction treatment;

[0009] b. The compound of formula (i) and the compound of formula (2) 1,3,5-tribromopyridine, palladium catalyst, potassium carbonate are placed in a Shrek tube, evacuated and then circulated with nitrogen three times, a certain proportion of organic solvent and water are added, and the reaction is carried out at 70° C. for 6 hours. The compound of formula (ii) is obtained by post-reaction treatment;

[0010] c. The compound of formula (ii) is mixed with 2-boronic acid pinacol anthraquinone, a palladium catalyst and potassium carbonate in a Shrek tube, evacuated and then circulated with nitrogen three times, a certain proportion of organic solvent and water are added, and the reaction is carried out at 90° C. for 6 h. The compound of formula (iii) is obtained by post-reaction treatment;

[0011] d. The compound of formula (ii) and the compound of formula (4), a palladium catalyst and potassium carbonate are placed in a Shrek tube, evacuated and then circulated with nitrogen three times, a certain proportion of organic solvent and water are added, and the reaction is carried out at 70° C. for 6 hours. The compound of formula (iv) is obtained by post-reaction treatment;

[0012] Furthermore, the palladium catalyst in step a is [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride; the organic solvent is deoxygenated tetrahydrofuran; and the potassium carbonate is powder.

[0013] Furthermore, the palladium catalyst in step b is [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride; the organic solvent is deoxygenated tetrahydrofuran; and the potassium carbonate is powder.

[0014] Furthermore, the palladium catalyst in step c is tetrakistriphenylphosphine palladium; the organic solvent is deoxygenated 1,4-dioxane; and the potassium carbonate is powder.

[0015] Furthermore, the palladium catalyst in step d is [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride; the organic solvent is deoxygenated tetrahydrofuran; and the potassium carbonate is powder. DETAILED DESCRIPTION

[0016] The present invention is described in detail below in conjunction with specific implementation modes.

[0017] The technical solution of the present invention is as follows:

[0018]

[0019] a. Weigh 50 mg (0.075 mmol) of the compound of formula (1), 38 mg (0.15 mmol) of biboric acid pinacol ester, and 2.74 mg (0.00375 mmol) of [1,1'-bis(diphenylphosphino)ferrocene] palladium dichloride in a 50 ml Shrek tube, pump three times through a tee, add 7.5 ml of tetrahydrofuran, 0.75 ml of water and 38 mg of potassium carbonate, react at 85 ° C for 6 h in a nitrogen atmosphere, extract, evaporate the organic phase, purify by column chromatography, the eluent is dichloromethane:n-hexane = 1:6, and recrystallize from dichloromethane and methanol to obtain 20.2 mg of the compound of formula (ⅰ), with a yield of 31.5%.

[0020] b. Take 50 mg (0.07 mmol) of the compound of formula (i) and 11 mg (0.035 mmol) of the compound of formula (2) 1,3,5-tribromopyridine, 5 mg (0.007 mmol) of [1,1'-bis(diphenylphosphino)ferrocene] palladium dichloride in a 50 ml Shrek tube, pump three times through a tee, add 15 ml of tetrahydrofuran, 1.5 ml of water and 24 mg of potassium carbonate, react at 70 ° C in a nitrogen atmosphere for 6 h, extract, evaporate the organic phase, purify by column chromatography, the eluent is dichloromethane:n-hexane = 1:5, recrystallize from dichloromethane and methanol to obtain 29.8 mg of the compound of formula (ⅱ), with a yield of 20.3%.

[0021] c. Take 70 mg (0.0522 mmol) of the compound of formula (ii) and 17.3 mg (0.1044 mmol) of 2-boric acid pinacol anthraquinone, 12.063 mg (0.01044 mmol) of tetrakistriphenylphosphine palladium in a 50 ml Shrek tube, add 30 ml of 1,4-dioxane, 8 ml of water and 7.2036 mg of potassium carbonate, react at 90 ° C for 6 h in a nitrogen atmosphere, extract, evaporate the organic phase, purify by column chromatography, the eluent is dichloromethane:n-hexane = 1:6, recrystallize from dichloromethane and methanol to obtain 7.2 mg of the compound of formula (iii), with a yield of 10.2%.

[0022] d. Take 20 mg (0.015 mmol) of the compound of formula (ii), 18.67 mg (0.04511 mmol) of the compound of formula (4), 2.196 mg (0.003 mmol) of [1,1'-bis(diphenylphosphino)ferrocene] palladium dichloride in a 50 ml Shrek tube, add 20 ml of tetrahydrofuran, 5 ml of water and 10.35 mg of potassium carbonate, react at 70 ° C in a nitrogen atmosphere for 6 h, extract, evaporate the organic phase, purify by column chromatography, the eluent is dichloromethane:n-hexane = 1:6, recrystallize from dichloromethane and methanol to obtain 5.3 mg of the compound of formula (iii), with a yield of 9.5%.

[0023] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Any simple modification, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention are within the scope of the technical solution of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] The present invention is further described below in conjunction with the accompanying drawings.

[0025] Figure 1 is the mass spectrum of compound (i) tetraphenyl borate;

[0026] Figure 2 is the H NMR spectrum of the monobromo-naphthene dimer of compound (ii);

[0027] Figure 3 is the mass spectrum of compound (ii) monobromo-naphthene dimer;

[0028] Figure 4 is the H NMR spectrum of the single benzene ring-connected anthraquinone-tetracene dimer of compound (iii);

[0029] Figure 5 is the mass spectrum of the single benzene ring-connected anthraquinone-tetracene dimer of compound (iii);

[0030] Figure 6 This is the mass spectrum of compound (iv) a double benzene ring-connected anthraquinone-tetracene dimer.

Claims

1. A type of anthraquinone-tetracene dimer connected by benzene rings, characterized in that: Its chemical structural formula is shown in formula (i), formula (ii), formula (iii) and formula (iv):

2. The method for preparing a type of anthraquinone-tetracene dimer connected by benzene rings as claimed in claim 1, characterized in that: The synthesis steps include: a. The compound of formula (1) is mixed with pinacol diboron, palladium catalyst and potassium carbonate in a Shrek tube, evacuated and then circulated with nitrogen three times, an organic solvent is added, and the reaction is carried out at 70°C for 6h. The compound of formula (i) is obtained by post-reaction treatment; b. The compound of formula (i) is mixed with 1,3,5-tribromopyridine, a palladium catalyst and potassium carbonate in a Shrek tube, evacuated and then circulated with nitrogen three times, an organic solvent is added, and the reaction is carried out at 70°C for 6h. The compound of formula (ii) is obtained by post-reaction treatment; c. The compound of formula (ii) is mixed with 2-boronic acid pinacol anthraquinone, a palladium catalyst and potassium carbonate in a Shrek tube, evacuated and then circulated with nitrogen three times, an organic solvent is added, and the reaction is carried out at 70°C for 6h. The reaction is treated to obtain the compound of formula (iii); d. The compound of formula (ii) and the compound of formula (4), a palladium catalyst and potassium carbonate are placed in a Shrek tube, evacuated and then circulated with nitrogen three times, an organic solvent is added, and the reaction is carried out at 70°C for 6 hours. The compound of formula (iv) is obtained by post-reaction treatment.

3. The anthraquinone-tetracene dimer connected by a benzene ring and a preparation method thereof according to claim 2, characterized in that In steps a and b, the palladium catalyst is [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride; the organic solvent is tetrahydrofuran; and the potassium carbonate is a 2 mol / L aqueous solution.

4. The anthraquinone-tetracene dimer connected by a benzene ring and a preparation method thereof according to claim 2, characterized in that The palladium catalyst in step c is tetrakis(triphenylphosphine)palladium, and the organic solvent is a mixed solvent of 1,4-dioxane:water=5:

1.

5. The anthraquinone-tetracene dimer connected by a benzene ring and the preparation method thereof according to claim 2, characterized in that The palladium catalyst in step d is tetrakis(triphenylphosphine)palladium, the organic solvent is tetrahydrofuran; and the potassium carbonate is a 2 mol / L aqueous solution.

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