CN110655657A - Synthesis method of metal-organic supramolecular polymer based on chiral terpyridine [3+3] structure - Google Patents

Abstract

The invention discloses a synthetic method of a metal-organic supramolecular polymer with a chiral terpyridine [3+3] structure, which comprises the following steps: sequentially adding pinene fused bis-terpyridyl carbazole ligand, zinc nitrate tetrahydrate and a solvent into a reactor; magnetically stirring in air atmosphere for reaction, and fully reacting in an oil bath kettle; after the reaction is finished, cooling to room temperature, adding excessive ammonium hexafluorophosphate, stirring until a large amount of solids are separated out, performing suction filtration, washing with water and drying to obtain a target product, completing the reaction in one step, and having the advantages of simple and convenient operation, high reaction efficiency and small dosage, thereby meeting the requirements of green chemical sustainable development.

Description

Synthesis method of metal-organic supramolecular polymer based on chiral terpyridine [3+3] structure

Technical Field

The invention belongs to the technical field of synthesis and application of organic compounds, and particularly relates to a synthesis method of a metal-organic supramolecular polymer based on a chiral terpyridine [3+3] structure.

Background

Chirality is ubiquitous in biology and nature and can be observed at varying levels of scale from subatomic and molecular to supramolecular, nano, asteroid scales and the like, to chiral properties (J.Sci.Am.,1990,262, 108-115; Angew.chem., Int.Ed.,2013,52, 2678-2683; chem.Rev.,2000,100, 1789-1816; John Wiley&Sons Ltd, New York, 2012), chirality at the molecular and supramolecular level is of crucial importance in scientific research at various physical scale levels from atom to molecule and supramolecule, as it is closely related to chemical, physical, biological, material and nanoscience, among other disciplines^[2]. Chirality has long been recognized at the molecular level and provides effective guidance for the design and development of drugs and functional molecules. Due to the rapid development of current supramolecular chemistry and molecular self-assembly, chirality at the supramolecular level has gradually attracted great attention from scientists.

In the supramolecular coordination compound or polymer structure, 2,2 ': 6 ', 2 ' -terpyridine (tpy) spontaneously forms coordination bonds with various metal ions (J.Am.chem.Soc.,2014,136,18149-²⁺E.g. Co²⁺,Ru²⁺,Zn²⁺,Pb²⁺,Ni²⁺,Fe²⁺The isocoordination forms a single-layer metal-organic supermolecule at an air/water interface, and the compound has the characteristic of electroluminescence. The plum topic group (nat. chem.,2018,9, 567-;nat. chem.,2018,9, 1815-; J.am.chem.Soc.,2018,140, 14087-; J.am.chem.Soc.,2014,136, 10499-one 10507) with a terpyridine building block and a metal M²⁺(M²⁺＝Fe²⁺,Zn²⁺,Cd²⁺,Ru²⁺Etc.) self-assemble to form a series of two-dimensional, three-dimensional supramolecular macrocyclic compounds.

Although pinene-fused chiral terpyridine-metal complexes have been well studied and widely used in catalytic asymmetric reactions (chem. Asian J.,2007,2, 411-415; chem. Asian J.,2007,2, 521-529; adv. Synth. Cat., 2007,349, 303-308; Journal of Molecular Catalysis A Chemical,2007,270,68-75), few reports have been made on the construction of chiral polymers. And because transition metals of octahedral coordination geometry have different coordination abilities (e.g., binding strength and reversibility), we have performed pinene-fused chiral terpyridine compounds herein with octadentate metal ion Cd²⁺Coordination studies of (3).

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides a synthesis method of a metal-organic supramolecular polymer with a chiral terpyridine [3+3] structure, which is simple and easy to implement, high in reaction efficiency and easy to purify.

In order to solve the technical problems, the invention adopts the following technical scheme:

chiral terpyridine [3+3]Method for the synthesis of a metal-organic supramolecular polymer of structure, comprising the following steps: sequentially adding pinene fused bis (terpyridyl) carbazole ligand, cadmium nitrate tetrahydrate and a solvent into a reactor; magnetically stirring in air atmosphere for reaction, and fully reacting in an oil bath kettle; after the reaction is finished, cooling to room temperature, adding excessive ammonium hexafluorophosphate, stirring until a large amount of solids are separated out, carrying out suction filtration, washing with water and drying to obtain a target product, namely the chiral terpyridine [3+3]]The molecular formula of the metal-organic supramolecular polymer with the structure is as follows: [ Cd ]₃L₃](PF₆)₆。

Further, the reactor is any glass container which can be sealed, and the whole reaction is carried out under an air atmosphere.

Further, the solvent is chloroform and absolute methanol in a volume ratio of 1: 2.5-1: 3.0.

Further, the mass ratio of the metal salt cadmium nitrate tetrahydrate to the pinene-fused bis (terpyridyl) carbazole ligand is 1: 1.

Further, the reaction temperature of the full reaction in the oil bath is 50 ℃, and the reaction time is 3 h.

Further, the counter ion is ammonium hexafluorophosphate ion, and the target product is obtained by directly filtering, filtering and drying without further purification.

A typical synthesis procedure is as follows: 6.2mg (2mmol) of Cd (NO)₃)₂·4H₂O was dissolved in 1.0mL of a methanol solution, and the solution (100. mu.L, 2.0. mu. mol) was added to a mixed solvent of chloroform (0.4mL) containing ligand L (2.2mg, 2.0. mu. mol) and anhydrous methanol (1.1mL) to dissolve the solution uniformly. The reaction was heated at 50 ℃ for 3 h. And after the reaction is completed, cooling to room temperature, adding excessive ammonium hexafluorophosphate, stirring until a large amount of solid is separated out, performing suction filtration, and washing a filter cake by using deionized water. In this process, NO₃ ^-Conversion of ions to PF₆ ^-Counter ion to give a yellow-green solid, the yield was calculated.

The preparation method of the pinene fused bis (terpyridyl) carbazole ligand L comprises the following steps: adding compound 11, chiral terpyridine 7, Pd (PPh) into Schlenk bottle under inert gas protection₃)₄Alkali and a solvent are pumped and flushed for three times, the reaction is carried out for 48 hours at 80 ℃ in an oil bath pot after the reaction is finished, the reaction system is cooled to room temperature, methylene dichloride is used for dissolving the reaction system, deionized water is used for washing an organic phase, the organic phase is dried by anhydrous sodium sulfate, filtered, the solvent is removed in vacuum, and the separation and purification are carried out by column chromatography, so that a brown yellow solid, namely the pinene fused bis-terpyridine carbazole ligand L is obtained, and the synthetic route is as follows:

wherein the mass ratio of the chiral terpyridine 7 to the compound 11 is 1: 2.0-1: 3.0; the amount of the tetrakis (triphenylphosphine) palladium is 10% of the amount of the chiral terpyridine 7; the alkali is an aqueous solution of sodium carbonate, the solvent is a mixed solution of toluene and tert-butyl alcohol, and the volume ratio of the toluene to the tert-butyl alcohol is 5: 2; the ratio of the amount of the base substance to the amount of the chiral terpyridine 7 substance is 1-10: 1.

The invention has the beneficial effects that: the invention relates to chiral terpyridine [3+3]The synthesis of the metal-organic supermolecular polymer with a structure provides a simple and easy method. The method utilizes chirally modified terpyridine construction unit and metal ion Cd²⁺And a supermolecular macrocyclic ring with a chiral structure is formed by means of self-assembly coordination. Compared with the traditional process, the method has the remarkable advantages that: (1) the new method adopts a simple and easily obtained solvent, and the volume of the solvent is micro; (2) the method avoids the purification problem in the traditional method; (3) the method adopts heating method, and greatly shortens time.

Drawings

FIG. 1 is a molecular model of the metal-organic supramolecular polymer based on chiral terpyridine [3+3] structure.

Detailed Description

The present invention will be further described with reference to the following examples. It is to be understood that the following examples are illustrative only and are not intended to limit the scope of the invention, which is to be given numerous insubstantial modifications and adaptations by those skilled in the art based on the teachings set forth above.

Example 1

The synthesis method of the metal-organic supramolecular polymer with the chiral terpyridine [3+3] structure comprises the following steps:

6.2mg of Cd (NO)₃)₂·4H₂O was dissolved in 1.0mL of a methanol solution, and the solution (100. mu.L, 2.0. mu. mol) was added to a mixed solvent of chloroform (0.4mL) containing ligand L (2.2mg, 2.0. mu. mol) and anhydrous methanol (1.1mL) to dissolve the solution uniformly. The reaction was heated at 50 ℃ for 3 h. Cooling to room temperature after the reaction is completed, adding excessive ammonium hexafluorophosphateSalt, stirring until a large amount of solid is separated out, filtering, and washing a filter cake by deionized water. In this process, NO₃ ^-Conversion of ions to PF₆ ^-Counter ion, gave a yellow-green solid in 95% yield.

¹H NMR(500MHz,CD₃CN-d₃)(δ,ppm)9.21(s,1H),9.04(s,2H),9.01(s,1H),8.95(s,2H),8.67(s,2H),8.43(d,J＝8.3Hz,1H),8.38(d,J＝7.6Hz,1H),7.98(dd,J＝8.3,3.7Hz,2H),7.66(s,2H),7.58(s,1H),7.57(s,2H),4.64(d,J＝5.2Hz,2H),3.23-3.10(m,8H),2.70-2.60(m,8H),2.26(d,J＝8.2Hz,5H),2.06(dd,J＝14.7,7.1Hz,2H),1.50(t,J＝9.3Hz,2H),1.45-1.40(m,2H),1.36(dt,J＝14.4,7.0Hz,3H),1.28(d,J＝10.5Hz,12H),1.09-1.04(m,4H),0.92(td,J＝7.2,2.2Hz,3H),0.45(d,J＝18.3Hz,12H).¹³C NMR(126MHz,CD₃CN-d₃)(δ,ppm)156.45,155.88,151.08,148.06,147.90,147.33,147.24,145.41,143.20,143.05,128.61,128.14,126.56,124.21,124.07,123.30,121.67,121.30,121.11,120.64,111.33,44.47,44.41,43.87,39.94,39.00,38.96,33.40,31.73,31.15,29.22,26.96,25.35,25.26,22.75,20.95,20.87,13.72.ESI-MS(m/z):601.4[M-6PF₆ ^-]⁶⁺(calcd m/z:601.5),750.7[M-5PF₆ ^-]⁵⁺(calcd m/z:750.7),974.7[M-4PF₆ ^-]⁴⁺(calcd m/z:974.7),1347.7[M-3PF₆ ^-]³⁺(calcd m/z:1347.9).

Example 2

The preparation method of the pinene fused bis (terpyridyl) carbazole ligand L comprises the following steps:

to a 50mL Schlenk flask, under inert gas, was added compound 11(150mg, 0.3mmol), chiral terpyridine 7(450mg,0.9mmol), Pd (PPh)₃)₄(35mg,0.03mmol)，Na₂CO₃(320mg,3mmol), toluene (10mL), t-butanol (4mL) and deionized water (4mL), followed by three puffs and a seal. The reaction was placed in an oil bath and allowed to react at 80 ℃ for 48 h. After the reaction is finished, cooling to room temperature, and using twoMethyl chloride dissolved the solids and the organic phase was washed with 50mL of deionized water. The organic phase was dried over anhydrous sodium sulfate, filtered and the solvent removed in vacuo. Thereafter, the crude product was purified by column chromatography (eluent: dichloromethane, dichloromethane/methanol ═ 100: 0.6) and further purified by column chromatography (eluent: chloroform) to obtain 140mg of a tan solid in a yield of 43%. Compound L is a novel compound, which compound has been prepared by¹H NMR、¹³C NMR、¹H-¹H COSY NMR、¹H^-1H NOESY NMR and ESI-MS.

¹H NMR(500MHz,CDCl₃)(δ,ppm)8.83(s,4H),8.78(s,2),8.48(s,4H),8.31(s,4H),8.10(d,J＝8.4Hz,2H),7.53(d,J＝8.6Hz,2H),4.39(t,J＝7.1Hz,2H),3.17(s,8H),2.92(t,J＝5.4Hz,4H),2.75(dt,J＝9.6,5.8Hz,4H),2.38(s,4H),2.01-1.91(m,2H),1.46(s,14H),1.38-1.34(m,2H),1.31(d,J＝9.5Hz,4H),0.89(t,J＝7.1Hz,3H),0.72(s,14H).¹³C NMR(126MHz,CDCl₃)(δ,ppm)156.40,154.99,150.81,145.57,145.25,142.84,141.46,129.85,125.57,123.61,120.75,119.72,118.33,109.19,44.61,43.46,40.22,39.35,33.10,31.92,31.57,29.03,26.99,26.09,22.55,21.46,14.02.HRMS(ESI)m/z calcd for[C₇₆H₇₉N₇+3H]³⁺364.2211,found 364.2216；calcd for[C₇₆H₇₉N₇+2H]²⁺545.8277,found 545.8267.

Example 3

The synthetic route of chiral terpyridine 7 is as follows:

synthesis of Compound 1

A reflux pipe, a drying pipe and a hollow plug are respectively arranged on a 1000mL three-mouth round-bottom flask, and a calcium chloride drying pipe is arranged at the upper end of the reflux pipe. Sodium metal (13.8g,0.6mol) was weighed out and cut into small pieces, which were added six to seven times to a three-necked flask containing absolute ethanol (300mL,5 mol). And after the metal sodium and the ethanol completely react and are cooled to room temperature, replacing the reflux pipe with a constant-pressure dropping funnel. At room temperature, a mixed solution of anhydrous acetone (22.8mL,0.3mol) and diethyl oxalate (86.4mL,0.6mol) was added dropwise to sodium ethoxide/ethanol, a yellow precipitate was formed during the dropwise addition, and when the remaining 1/4 was added dropwise, the mixture was transferred to a 60 ℃ oil bath until the dropwise addition was completed. During this process, the yellow solid dissolved and a new solid formed. After stirring for 1h, cool to room temperature, add concentrated hydrochloric acid (120mL) and deionized water (60mL), and stir at 50 ℃ for 24 h. After completion of the reaction, the ethanol/water solution (about 270mL) was distilled off under reduced pressure (the temperature should not be too high during distillation under reduced pressure, and bumping is likely to occur). After cooling to room temperature, concentrated hydrochloric acid (30mL) and deionized water (180mL) were added and stirred at 50 ℃ for 72 h. After cooling to room temperature, suction filtration was carried out, and the filter cake was repeatedly washed with ice water and acetone. Dissolving the obtained solid with appropriate amount of water, adding small amount of active carbon, heating to boil, and hot filtering to obtain filtrate. The filtrate was cooled to precipitate a white-yellow solid, which was filtered and dried to give 32g of a pale yellow powdery solid with a yield of 55.3%. Compound 1 was used in the next step without purification.

Synthesis of Compound 2

Under ice bath conditions, compound 1(25g) and ammonia (250mL) were added to a 500mL round bottom flask, and after the addition was completed, the mixture was stirred at room temperature for 48h, and during the reaction, the solution gradually changed from turbid to red, clear and transparent solution. After completion of the reaction, it was concentrated in vacuo. Deionized water (30mL) was added to dissolve the residue, boiled and decolorized with activated carbon, and filtered hot with suction to give a filtrate. Cooling to room temperature, and dropwise adding concentrated hydrochloric acid until no white or light yellow solid is precipitated. Filtering to obtain white solid, adding deionized water, boiling, cooling, filtering, and drying to obtain 23.5g white powdery compound 2 with a yield of 95.5%.

4-hydroxypyridine-2,6-dicarboxylic acid(2)

White solid；Mp 259-260℃；

¹H NMR(400MHz,DMSO-d₆)(δ,ppm)7.57(s,2H)；¹³C NMR(100MHz,DMSO-d₆)(δ,ppm)165.7,115.2,113.9,112.9.

Synthesis of Compound 4

In a 250mL round bottom flask, n-hexane (100mL) was added and liquid bromine (7.6mL,150mmol) and phosphorus tribromide (17mL,180mmol) were added sequentially with stirring. Stirring for 1h at room temperature to obtain bright yellow phosphorus pentabromide solid. Removing excessive n-hexane solution, repeatedly washing with n-hexane or petroleum ether, and vacuum drying. To the above yellow powdery solid was added compound 2(10g,54.6g), and the mixture was heated under reflux at 90 ℃ for 4 hours (calcium chloride drying tube attached to reflux tube). After the reaction was completed, it was cooled to room temperature, and anhydrous dichloromethane (20mL) was added to the reaction flask, stirred for 30min, and filtered. A mixed solution of anhydrous dichloromethane (50mL) and tetrahydropyrrole (17.2mL,205mmol) was added dropwise under an ice-water bath. After the addition, the mixture was stirred at room temperature for 2 hours. Thereafter, the reaction solution was poured into dilute hydrochloric acid (100mL,2M), extracted with 3X 50mL of dichloromethane, and the organic phase was collected. The organic phase was washed with 3X 100mL of water. The organic phase was dried over anhydrous sodium sulfate and concentrated in vacuo. The residue was purified by column chromatography (neutral alumina, eluent: petroleum ether: dichloromethane ═ 400:100 gradient elution) to afford 6.5g of compound 4 as a white or yellow solid in 52% yield.

(4-hydroxypyridine-2,6-diyl)bis(pyrrolidin-1-ylmethanone)(4)

White solid；Mp 90-93℃；

¹H NMR(400MHz,CDCl₃)(δ,ppm)8.04(s,2H),3.72-3.61(m,2H),2.00-1.87(m,2H)；¹³C NMR(100MHz,CDCl₃)(δ,ppm)164.7,153.9,134.5,128.3,49.1,47.0,26.6,24.0.

Synthesis of Compound 5

To a 50mL Schlenk cooled by high temperature baking under inert gas atmosphere, Compound 4(1.5g,4.26mmol) and anhydrous tetrahydrofuran (20mL) were added. Methyl magnesium chloride solution (4mL,3M,8.52mmol) was added dropwise at-5 deg.C under argon shield and reacted for 6 h. After the reaction was complete, it was quenched with dilute hydrochloric acid (15mL, 2M). The reaction solution was poured into a separatory funnel, extracted with 3 × 10mL of dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate and concentrated under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: petroleum ether: ethyl acetate ═ 40: 1 gradient elution) to give 0.67g of a white snowflake solid in 65% yield.

1,1'-(4-bromopyridine-2,6-diyl)bis(ethan-1-one)(5)

White solid；Mp 84-85℃；

¹H NMR(400MHz,CDCl₃)(δ,ppm)8.35(s,2H),2.78(s,6H)；¹³C NMR(100MHz,CDCl₃)(δ,ppm)198.1,153.5,135.4,128.0,25.6.

Synthesis of Compound 6

To a 50mL round bottom flask was added compound 5(0.968g,4mmol), anhydrous pyridine (6.4mL,8mmol) was added dropwise until the solid dissolved, elemental iodine (2.13g,8.4mmol) was added, and the mixture was heated to 100 ℃ and stirred for 3 h. After the reaction, the mixture is cooled to room temperature, 20mL of absolute ethyl alcohol is added, ultrasonic treatment and suction filtration are carried out, then a small amount of absolute ethyl alcohol is used for recrystallization, suction filtration and drying, and 2.33g of yellow powdery solid 6 is obtained, wherein the yield is 90%. The compound is a new compound which has been obtained by IR,¹H NMR、¹³C NMR and the like.

1,1'-((4-bromopyridine-2,6-diyl)bis(2-oxoethane-2,1-diyl))bis(pyridin-1-ium)(6)

Bright yellow solid；Mp 175-176℃；

IR(ν,cm^-1)3408,1714,1632,1486,1344,1273,1198,1050,991,871,776,671；

¹H NMR(400MHz,DMSO-d₆)(δ,ppm)9.07(d,J＝5.8Hz,4H),8.80(t,J＝7.9Hz,2H),8.63(s,2H),8.34(t,J＝6.9Hz,4H),6.60(s,4H)；¹³C NMR(100MHz,DMSO-d₆)(δ,ppm)189.3,151.0,146.8,146.3,135.8,129.0,66.4；HRMS(ESI)m/z calcd for C₁₉H₁₆BrI₂N₃O₂198.5208[M-2I]²⁺；found 198.5207.

Synthesis of Compound 7

To a high temperature baked and cooled 50mL Schlenk flask, compound 6(1.64g,2.52mmol), ammonium acetate (0.85g,5.38mmol), formamide (15mL,94.4mmol), and (1R) - (-) -myrtenal (770. mu.L, 5.10mmol) were added sequentially under inert gas. The mixture was stirred at room temperature for 30min, after stirring well, at 80 ℃ for 12 h. After the reaction, the reaction mixture was cooled to room temperature, filtered, and the solid was washed with ice water and dried. The resulting solid was passed through a elution column (neutral alumina, eluent: ethyl acetate). ReducingConcentrated under pressure, dried and weighed to give 818mg of a tan powdery solid with a yield of 65%. The compound is a new compound which has been obtained by IR,¹H NMR、¹³C NMR and the like.

(6R,6'R,8R,8'R)-3,3'-(4-bromopyridine-2,6-diyl)bis(7,7-dimethyl-5,6,7,8-tetrahy dro-6,8-methanoisoquinoline)(7)

Brownish yellow solid；Mp 189-191℃；

IR(ν,cm^-1)2929,1545,1481,1358,1269,1052,876,750,669,604；

¹H NMR(400MHz,CDCl₃)(δ,ppm)8.56(s,2H),8.30(s,2H),8.23(s,2H),3.13(d,J＝9.5Hz,4H),2.90(t,J＝5.7Hz,2H),2.77-2.71(m,2H),2.40-2.33(m,2H),1.45(s,6H),1.27(d,J＝9.5Hz,2H),0.68(s,6H)；¹³C NMR(100MHz,CDCl₃)(δ,ppm)157.0,153.4,145.6,143.6,134.9,123.6,120.8,44.6,40.1,39.3,33.1,31.8,26.0,21.5,21.4；HRMS(ESI)m/zcalcd for C₂₉H₃₀BrN₃ 500.1696[M+H]⁺；found 500.1700.

Example 4

The synthesis route of the boronic acid pinacol ester compound 11, namely 9-hexyl-3, 6-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) -9H-carbazole is as follows:

synthesis of Compound 9

Compound 8(3.30g,20mmol) and KOH (2.96g,52.8mmol) were dissolved in DMF (40mL) at room temperature and stirred for 60 min. Then, n-C was added dropwise₆H₁₃Br (3.30g,20mmol) and the reaction mixture was stirred at room temperature for 48 h. After this time, the mixture was poured into deionized water and extracted with chloroform, and the organic phase was dried over anhydrous sodium sulfate. The solvent was removed by distillation under the reduced pressure, and the crude product was purified by silica gel column chromatography using n-hexane to give the compound 9 in a yield of 90.9%. The product is a known compound¹H NMR confirmed.

9-hexyl-9H-carbazole(9)

Yellow solid；Mp 61-62℃；

¹H NMR(400MHz,CDCl₃)(δ,ppm)8.10(d,J＝7.7Hz,2H),7.46(t,J＝7.4Hz,2H),7.40(d,J＝8.0Hz,2H),7.23(dd,J＝12.6,5.1Hz,3H),4.29(t,J＝7.3Hz,2H),1.94-1.79(m,2H),1.44-1.20(m,6H),0.86(t,J＝6.9Hz,3H).

Synthesis of Compound 10

Compound 9(1.0g,3.98mmol) was dissolved in chloroform (30mL) and N-bromosuccinimide (NBS) (1.42g,7.96mmol) was added slowly. The above solution was stirred in an oil bath at 40 ℃ for 12h, after which the mixture was quenched with water and extracted with dichloromethane. The organic phase was collected, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The crude product was isolated and purified by using a silica gel column and hexane as a developing agent to obtain 1.56g of a white pure solid with a yield of 96%.

3,6-dibromo-9-hexyl-9H-carbazole(10)

White solid；Mp 101-102℃；

¹H NMR(400MHz,CDCl₃)(δ,ppm)8.13(s,2H),7.54(d,J＝8.4Hz,2H),7.26(d,J＝7.7Hz,2H),4.23(t,J＝6.7Hz,2H),1.81(t,J＝6.3Hz,2H),1.29(s,6H),0.85(s,3H)；¹³C NMR(100MHz,CDCl₃)(δ,ppm)139.20,128.91,123.34,123.15,111.85,110.30,43.25,31.45,28.76,26.83,22.47,13.95.

Synthesis of Compound 11

Under the protection of inert gas, compound 10(1.2g,2.9mmol), B are added in turn to a 50mL Schlenk bottle which is baked and cooled at high temperature₂Pin₂(1.4g,5.6mmol (1.9 times the amount)), Pd (PPh)₃)₂Cl₂(0.06 times amount) and KOAc (6 times amount), and DMSO (20mL) was added as a solvent. The mixture was heated to 85 ℃ and reacted for 12 h. After the reaction, the reaction system was cooled to room temperature, filtered to remove insoluble matter, and washed with chloroform. The reaction mixture was then washed with deionized water (3X 50mL), the organic layer was collected and dried over anhydrous sodium sulfate, filtered with suction. After removal of the solvent in vacuo, the crude product was purified by column separation (eluent: hexane to hexane/dichloromethane 2/1 to 1/1 as eluent) to yield870mg of a white solid, yield 60%.

9-hexyl-3,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole(11)

White solid；Mp>300℃；

¹H NMR(400MHz,CDCl₃)(δ,ppm)8.66(s,2H),7.90(d,J＝7.9Hz,2H),7.39(d,J＝7.9Hz,2H),4.29(t,J＝6.4Hz,2H),1.85(m,2H),1.39(s,30H),0.84(s,3H)；¹³C NMR(100MHz,CDCl₃)(δ,ppm)142.61,131.92,128.00,122.77,118.80,108.05,83.46,43.08,31.52,28.85,26.84,24.91,22.47,13.96.

The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (10)

1. Chiral terpyridine [3+3]Method for the synthesis of a metal-organic supramolecular polymer of structure, characterized in that it comprises the following steps: sequentially adding pinene fused bis (terpyridyl) carbazole ligand L, cadmium nitrate tetrahydrate and a solvent into a reactor; magnetically stirring in air atmosphere for reaction, and fully reacting in an oil bath kettle; after the reaction is finished, cooling to room temperature, adding excessive ammonium hexafluorophosphate, stirring until a large amount of solids are separated out, carrying out suction filtration, washing with water and drying to obtain a target product, namely the chiral terpyridine [3+3]]The molecular formula of the metal-organic supramolecular polymer with the structure is as follows: [ Cd ]₃L₃](PF₆)₆。

2. The method of synthesis of metal-organic supramolecular polymers of chiral terpyridine [3+3] structure according to claim 1, characterized in that: the reactor is any glass container which can be sealed, and the whole reaction is carried out under an air atmosphere.

3. The method of synthesis of metal-organic supramolecular polymers of chiral terpyridine [3+3] structure according to claim 1, characterized in that: the solvent is chloroform and anhydrous methanol with the volume ratio of 1: 2.5-1: 3.0.

4. The method of synthesis of metal-organic supramolecular polymers of chiral terpyridine [3+3] structure according to claim 1, characterized in that: the mass ratio of the cadmium nitrate tetrahydrate to the pinene fused bis (terpyridyl) carbazole ligand is 1: 1.

5. The method of synthesis of metal-organic supramolecular polymers of chiral terpyridine [3+3] structure according to claim 1, characterized in that: the reaction temperature of the full reaction in the oil bath pot is 50 ℃, and the reaction time is 3 h.

6. The chiral terpyridine [3+3] of claim 1]The synthesis method of the metal-organic supramolecular polymer with the structure is characterized in that the preparation method of the pinene fused bis (terpyridyl) carbazole ligand L is as follows: adding compound 11, chiral terpyridine 7, Pd (PPh) into Schlenk bottle under inert gas protection₃)₄Alkali and a solvent are pumped and flushed for three times, the reaction is carried out for 48 hours at 80 ℃ in an oil bath pot after the reaction is finished, the reaction system is cooled to room temperature, methylene dichloride is used for dissolving the reaction system, deionized water is used for washing an organic phase, the organic phase is dried by anhydrous sodium sulfate, filtered, the solvent is removed in vacuum, and the separation and purification are carried out by column chromatography, so that a brown yellow solid, namely the pinene fused bis-terpyridine carbazole ligand L is obtained, and the synthetic route is as follows:

7. the method for synthesizing a metal-organic supramolecular polymer of chiral terpyridine [3+3] structure according to claim 6: the mass ratio of the chiral terpyridine 7 to the compound 11 is 1: 2.0-1: 3.0.

8. The method for synthesizing a metal-organic supramolecular polymer of chiral terpyridine [3+3] structure according to claim 6: the amount of tetrakis (triphenylphosphine) palladium used was 10% of the amount of chiral terpyridine 7 material.

9. The method for synthesizing a metal-organic supramolecular polymer of chiral terpyridine [3+3] structure according to claim 6: the alkali is sodium carbonate aqueous solution, the solvent is a mixed solution of toluene and tert-butyl alcohol, and the volume ratio of toluene to tert-butyl alcohol is 5: 2.

10. The method of synthesizing metal-organic supramolecular polymers of chiral terpyridine [3+3] structure according to claim 6, characterized in that: the ratio of the amount of the base substance to the amount of the chiral terpyridine 7 substance is 1-10: 1.