Compound constructed based on 1, 10-phenanthroline as well as synthesis method and application thereof

Abstract

The invention designs and synthesizes a compound constructed on the basis of 1, 10-phenanthroline and 4-(9-carbazolyl) phenylboronic acid, and the compound is obtained through a Suzuki-Miyaura reaction in one step. The method has the advantages of mild reaction conditions, simple reaction steps, high yield of finished products and the like. Due to the existence of C-Hpi interaction among molecules, the compound forms a three-dimensional network structure with a cavity in a crystalline state, so that the small-molecule compound has excellent properties which are the same as those of a traditional macrocyclic aromatic hydrocarbon main body; and under the condition of no induction, self-assembly can occur to form a non-covalent bond molecular pipeline for adsorbing and packaging benzene series pollutants. In the adsorption process, the energy consumption is low, the adsorption time is short, the equipment requirement is low, the selected crystalline material is easy to synthesize, the yield is high, the stability is strong, the adsorption quantity of benzene series pollutants is high, and the adsorption effect is good.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic synthetic chemistry, and relates to a compound constructed based on 1,10-phenanthroline, and a synthesis method and application thereof. Background Art

[0002] Supramolecular chemistry is a newly emerging interdisciplinary subject that integrates organic chemistry, analytical chemistry, inorganic chemistry and polymer chemistry. It mainly studies the molecular aggregation with specific functions formed between molecules through non-covalent interactions such as hydrogen bonds, metal coordination, host-guest interactions, and π-π stacking.

[0003] 1,10-Phenanthroline (phen) is one of the most commonly used ligands in coordination chemistry due to its strong affinity for metals in various oxidation states. Its polyaromatic structure is robust and rigid, which gives it fascinating properties in many fields (luminescent coordination scaffolds, catalysis, sensors, therapeutics, etc.). In summary, 1,10-phenanthroline is used in almost every aspect of chemistry. One of its fascinating features is that each pair of carbon atoms has a specific reactivity, so each pair of carbon atoms can be functionalized with different groups, resulting in a multifunctional array. In addition, each position in these pairs can be distinguished, resulting in asymmetric systems with huge versatility.

[0004] Carbazole, also known as 9-azafluorene and iminodiphenylene, is mainly used in the manufacture of dyes, chemical reagents, explosives, pesticides, lubricants, rubber antioxidants, etc.

[0005] Benzene series (BTEX) is a type of volatile organic pollutants (VOCs) with a high content. It has a high evaporation rate at room temperature, is easy to volatilize, and has high chemical reactivity. It is an important precursor of ozone (O3) and secondary organic pollutants (SOA) in ambient air. Benzene, toluene, o-, m-xylene and p-xylene are the main pollutants in BTEX. They can usually represent BTEX to study its pollution characteristics. Its sources are mainly related to petrochemical products and industries. Long-term exposure to BTEX in ambient air will irritate human skin and mucous membranes, and cause certain damage to the human respiratory system, hematopoietic system and nervous system. In addition, BTEX has a certain carcinogenic risk.

[0006] At present, there are many macrocyclic aromatic hydrocarbons used to adsorb benzene pollutants, but there are few studies on the adsorption of benzene pollutants by small molecule self-assembly. Therefore, it is of great research value to realize the construction of compounds based on 1,10-phenanthroline and its application in the adsorption of benzene pollutants. Summary of the invention

[0007] The present invention aims to provide a small molecule compound constructed based on 1,10-phenanthroline and 4-(9-carbazolyl)phenylboronic acid as an efficient adsorption material for benzene-based pollutants (benzene, toluene, o-, m-, and p-xylene). The compound can self-assemble into a typical supramolecular organic framework (SOF) material without any induction. Compared with traditional macrocyclic aromatic hydrocarbons, the material has the advantages of simple synthesis and high yield. The cavity formed by the CH⋅⋅⋅π interaction between molecules can be used to solve the technical problems of existing benzene-based pollutant adsorption materials, such as slow adsorption speed, low adsorption capacity, and inactivation due to water absorption.

[0008] The present invention is based on the compound constructed from 1,10-phenanthroline, and the structural formula is: .

[0009] The compound based on 1,10-phenanthroline and 4-(9-carbazolyl)phenylboronic acid involved in the present invention is obtained in one step by Suzuki-Miyaura reaction. Specifically, it comprises the following steps: Potassium carbonate and tetrakistriphenylphosphine palladium are added to a mixed solution of 1,4-dioxane and water in which 1,10-phenanthroline and 4-(9-carbazolyl)phenylboronic acid are dissolved, and the mixture is reacted at 90° C. for 24 hours under nitrogen protection. After the reaction is completed, the mixture is washed with distilled water and separated by column chromatography to obtain the compound.

[0010] Wherein: 1,4-dioxane and water are solvents in a ratio of 4:1 to 6:1, the molar ratio of 1,10-phenanthroline to 4-(9-carbazolyl)phenylboronic acid is 1:2 to 1:2.5, the molar amount of potassium carbonate is 1 to 1.5 times the molar amount of 1,10-phenanthroline, and the molar amount of the catalyst tetrakistriphenylphosphine palladium is 0.1 to 0.2 times the molar amount of 1,10-phenanthroline.

[0011] The synthetic route is as follows: The small molecule compound provided by the present invention has high stability in the Suzuki-Miyaura reaction system using general halogenated hydrocarbons as reaction solvents and tetrakistriphenylphosphine palladium as catalyst. The compound can also be self-assembled into a typical supramolecular organic framework (SOF) material without any induction, and has good application prospects in the fields of supramolecular assembly, adsorption separation, fluorescent sensors and functional materials.

[0012] Compared with traditional macrocyclic aromatic hydrocarbons, the present invention has simpler preparation conditions, fewer reaction steps, simpler operation, and higher yield. Due to the existence of intermolecular CH⋅⋅⋅π interactions, the compound forms a three-dimensional network structure with cavities in the crystalline state, which makes the small molecule compound have the same excellent properties as the traditional macrocyclic aromatic hydrocarbon main body.

[0013] The small molecule compound provided by the present invention has a central symmetrical structure of a nanometer-sized electron-deficient cavity in a crystalline state, which is conducive to the adsorption and separation of molecules with similar structures, such as aromatic hydrocarbons and cycloaliphatic compounds.

[0014] The compound constructed based on 1,10-phenanthroline and 4-(9-carbazolyl)phenylboronic acid provided by the present invention has the characteristic of being able to form a non-covalent bond molecular pipeline, and as a high-efficiency adsorption material for benzene-based pollutants, etc., it has potential application value in supramolecular assembly, adsorption separation, etc. The compound constructed based on 1,10-phenanthroline and 4-(9-carbazolyl)phenylboronic acid can form a non-covalent bond molecular pipeline for adsorption and encapsulation of benzene-based pollutants, wherein the compound and benzene can form a 1:3 host-guest compound, that is, each host small molecule compound adsorbs 3 guest molecules; the compound and toluene, o-xylene, m-xylene and p-xylene can form a 1:1 host-guest complex, that is, each host small molecule compound adsorbs 1 guest molecule, that is, one cavity structure formed by two host small molecule compounds can encapsulate two guest molecules. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 The hydrogen nuclear magnetic resonance spectrum of the compound constructed based on 1,10-phenanthroline and 4-(9-carbazolyl)phenylboronic acid of the present invention.

[0016] Figure 2 The carbon nuclear magnetic resonance spectrum of the compound constructed based on 1,10-phenanthroline and 4-(9-carbazolyl)phenylboronic acid of the present invention.

[0017] Figure 3 The mass spectrum of the compound constructed based on 1,10-phenanthroline and 4-(9-carbazolyl)phenylboronic acid of the present invention.

[0018] Figure 4 The single crystal structure diagram and the molecular nanochannel crystal structure diagram of the compound constructed based on 1,10-phenanthroline and 4-(9-carbazolyl)phenylboronic acid of the present invention.

[0019] Figure 5 The eutectic structures are observed from the a-axis (a), b-axis (b) and c-axis (c) after the pipes formed by self-assembly of the compounds constructed based on 1,10-phenanthroline and 4-(9-carbazolyl)phenylboronic acid adsorb and encapsulate benzene.

[0020] Figure 6The eutectic structures are observed from the a-axis (a), b-axis (b) and c-axis (c) after the pipeline formed by self-assembly of the compound constructed based on 1,10-phenanthroline and 4-(9-carbazolyl)phenylboronic acid of the present invention adsorbs and encapsulates toluene.

[0021] Figure 7 The eutectic structures are observed from the a-axis (a), b-axis (b) and c-axis (c) after the pipes formed by self-assembly of the compounds constructed based on 1,10-phenanthroline and 4-(9-carbazolyl)phenylboronic acid adsorb and encapsulate o-xylene.

[0022] Figure 8 The eutectic structures are observed from the a-axis (a), b-axis (b) and c-axis (c) after the pipes formed by self-assembly of the compounds constructed based on 1,10-phenanthroline and 4-(9-carbazolyl)phenylboronic acid adsorb and encapsulate m-xylene.

[0023] Fig. 9 The eutectic structures are observed from the a-axis (a), b-axis (b) and c-axis (c) after the pipes formed by self-assembly of the compounds constructed based on 1,10-phenanthroline and 4-(9-carbazolyl)phenylboronic acid adsorb and encapsulate p-xylene.

[0024] Fig.10 The graph is a comparison of the hydrogen spectrum shift of the main compound (a) constructed based on 1,10-phenanthroline and 4-(9-carbazolyl)phenylboronic acid, benzene (c), and the compound (b) after adsorbing benzene.

[0025] Fig.11 The graph is a comparison of the hydrogen spectrum shift of the main compound (a) constructed based on 1,10-phenanthroline and 4-(9-carbazolyl)phenylboronic acid, toluene (c), and the compound (b) after adsorbing toluene.

[0026] Fig.12 The graph is a comparison of the hydrogen spectrum shift of the main compound (a) constructed based on 1,10-phenanthroline and 4-(9-carbazolyl)phenylboronic acid, o-xylene (c), and the compound (b) after adsorbing o-xylene.

[0027] Fig.13 The graph is a comparison of the hydrogen spectrum shift of the main compound (a) constructed based on 1,10-phenanthroline and 4-(9-carbazolyl)phenylboronic acid, m-xylene (c), and the compound (b) after adsorbing m-xylene.

[0028] Fig.14 The graph is a comparison of the hydrogen spectrum shift of the main compound (a) constructed based on 1,10-phenanthroline and 4-(9-carbazolyl)phenylboronic acid, p-xylene (c), and the compound (b) after adsorbing p-xylene.

[0029] Fig.15 This is the curve of the solid-gas adsorption of benzene pollutant vapor to compounds changing with time at 293 K. DETAILED DESCRIPTION

[0030] The specific implementation methods of this product are further described below with reference to examples. The instruments and reagents used are conventional products available on the market unless otherwise specified.

[0031] Example 1 Synthesis of compound 1 based on 1,10-phenanthroline and 4-(9-carbazolyl)phenylboronic acid Potassium carbonate (273 mg, 1.5 mmol) and tetrakistriphenylphosphine palladium (231 mg, 0.2 mmol) were added to a mixed solution of 1,4-dioxane and water (18 ml, 1,4-dioxane: water = 5:1, v / v) in which 1,10-phenanthroline (338 mg, 1 mmol) and 4-(9-carbazolyl)phenylboronic acid (718 mg, 2.5 mmol) were dissolved, and the mixture was reacted at 90°C under nitrogen protection for 24 hours. After the reaction was completed, the mixture was extracted with a CH2Cl2 / H2O system and separated by column chromatography (petroleum ether: ethyl acetate = 40:1, v / v) to obtain a light yellow solid product (compound 1, 464 mg, 70%).

[0032] 1 H NMR (400 MHz, Chloroform- d ) δ 8.70 (d, J = 8.5 Hz, 4H), 8.42 (d, J =8.4 Hz, 2H), 8.26 (d, J = 8.4 Hz, 2H), 8.16 (d, J = 7.7 Hz, 4H), 7.88 (s, 2H), 7.82 (d, J = 8.5 Hz, 4H), 7.55 (d, J = 8.2 Hz, 4H), 7.48 – 7.42 (m, 4H), 7.33 –7.28 (m, 4H). ; 13 C NMR (151 MHz, Chloroform- d) δ 156.43, 149.09, 147.52,136.78, 129.32, 128.59, 127.56, 125.63, 124.82, 123.34, 123.22. ;ESI-HRMS (m / z): calcdfor C 48 H 30 N4663.2543 (M + H + ); found 663.2527 (M + H + ). ( 1 H NMR, 13 C NMR and ESI-HRMS spectra are shown in Figures 1-3 ). For the single crystal cultivation of compound 1 constructed based on 1,10-phenanthroline and 4-(9-carbazolyl)phenylboronic acid, 6 mg of pure compound 1 was weighed and placed in a 10 mL glass vial, 2.5 mL of analytical grade dichloromethane was added and heated to dissolve until the solution was clear and transparent, and then 2.5 mL of analytical grade n-hexane was added to the glass bottle, the bottle cap was loosened, and single crystal cultivation was performed by slowly evaporating the solvent, and the bottle was placed in a cool place. Do not shake the glass bottle during observation.

[0033] The single crystal structure of compound 1 based on 1,10-phenanthroline and 4-(9-carbazolyl)phenylboronic acid is shown in Figure 4 The cavity formed is shaped like a "bow tie". The long axis of the cavity is 12.4Å and the short axis is 7.693Å (as shown in Figure 4d). The entire single crystal has a central symmetry, but the upper and lower molecules are staggered and not in the same plane. The stacking structure of the crystal has the property of forming a non-covalent molecular channel due to the C-H···π force between the two adjacent molecules (as shown in Figure 4a), which has potential application value in supramolecular assembly, adsorption separation, etc. Figure 5-9 The eutectic structure of five benzene-based pollutants is formed by non-covalent molecular channel adsorption and encapsulation of compounds constructed based on 1,10-phenanthroline and 4-(9-carbazolyl)phenylboronic acid. Among them, it can form a 1:3 host-guest complex with benzene, and each cavity encapsulates 3 guest molecules. It can form a 1:1 host-guest complex with other benzene-based compounds, and each cavity encapsulates 2 guest molecules.

[0034] Figure 10-14 The hydrogen spectrum shift comparison of the molecular entity, benzene pollutants, and the molecular entity after adsorption of benzene pollutants shows that the peak of benzene pollutants shows a low-field shift in the spectrum, but because the main molecule is a single molecule in the deuterated reagent, the shift of the peak of benzene pollutants in the spectrum is not obvious.

[0035] Example 2 Adsorption of benzene-based pollutants by host molecule 1 In the gas phase independent experiment of the efficient adsorption of benzene pollutant vapor by compound 1 constructed based on 1,10-phenanthroline and 4-(9-carbazolyl)phenylboronic acid, a 5.00 mL open vial containing 5.00 mg of activated host molecule adsorbent was placed in a 20.00 mL sealed vial containing 1.00 mL of benzene, toluene, o-, m-, and p-xylene. The relative absorption of the activated host molecule adsorbent for the five benzene pollutants was measured by the molar amount of vapor adsorbed by the benzene pollutants and the molar amount of vapor released by heating the crystals. Before the measurement, the crystals were heated at 80 ° C for half an hour to remove the vapor physically adsorbed on the surface. Fig.15 The curve of the solid-gas adsorption cycle experiment of benzene pollutant vapor on the main molecule at 293K changes with time. It takes about 2 hours for the crystal to reach the saturation point after adsorbing benzene pollutants. At the saturation point, according to the experimental results, the molar ratio of benzene adsorbed by the main molecule is 1:3, and the molar ratio of other pollutants adsorbed is 1:1, which is consistent with the crystal characterization results. After repeated use for 5 times, the adsorption retention time of benzene pollutants has not changed significantly, indicating that the adsorption material prepared by the compound in the present invention has a high recycling rate.

Claims

1. A compound based on 1,10-phenanthroline, characterized in that: The structural formula of the compound is shown below: 。 2. A method for synthesizing a compound constructed based on 1,10-phenanthroline as claimed in claim 1, characterized in that: Potassium carbonate and tetrakistriphenylphosphine palladium are added to a mixed solution of 1,4-dioxane and water in which 1,10-phenanthroline and 4-(9-carbazolyl)phenylboronic acid are dissolved, and the mixture is reacted at 80-100° C. for 20-25 hours under nitrogen protection. After the reaction is completed, the mixture is washed with distilled water and separated by column chromatography to obtain the compound.

3. The method for synthesizing a compound constructed based on 1,10-phenanthroline as claimed in claim 2, characterized in that: The volume ratio of 1,4-dioxane to water is 4:1-6:

1.

4. The method for synthesizing a compound constructed based on 1,10-phenanthroline as claimed in claim 2, characterized in that: The molar ratio of 1,10-phenanthroline to 4-(9-carbazolyl)phenylboronic acid is 1:2 to 1:2.

5.

5. The method for synthesizing a compound constructed based on 1,10-phenanthroline as claimed in claim 2, characterized in that: The molar amount of potassium carbonate is 1 to 1.5 times the molar amount of 1,10-phenanthroline.

6. The method for synthesizing a compound constructed based on 1,10-phenanthroline as claimed in claim 2, characterized in that: The molar amount of the tetrakistriphenylphosphine palladium is 0.1 to 0.2 times the molar amount of 1,10-phenanthroline.

7. Use of the compound constructed based on 1,10-phenanthroline as claimed in claim 1 in adsorbing benzene pollutants.

8. The use of the compound constructed based on 1,10-phenanthroline in adsorbing benzene pollutants as claimed in claim 7, characterized in that: The benzene pollutant is at least one of benzene, toluene, o-xylene, m-xylene and p-xylene.

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