CN114524948A

CN114524948A - 3D supramolecular material with various coordination configurations and preparation method and application thereof

Info

Publication number: CN114524948A
Application number: CN202210251071.3A
Authority: CN
Inventors: 张哲�; 白栖霞; 谢廷正; 伍暾; 王平山
Original assignee: Guangzhou University
Current assignee: Guangzhou University
Priority date: 2022-03-15
Filing date: 2022-03-15
Publication date: 2022-05-24

Abstract

The invention belongs to the technical field of chemical synthesis, and particularly relates to a supramolecular material capable of forming various configurations when the same ligand is coordinated with different transition metals and a preparation method thereof. The invention firstly utilizes the characteristic of high stability of metallic ruthenium to synthesize a novel catalyst containing ruthenium<tpy‑Ru²⁺‑tpy>When the four-arm metal organic ligand L is assembled with transition metals with different coordination strengths, different three-dimensional metal organic supermolecular configurations are formed. Wherein the metal ions (Co, Zn) with strong ligand binding capacity are utilized to form a larger structure [ M₈L₄]Whereas metal ions (Cd) with weak ligand binding capacity lead to the formation of smaller structures [ M₆L₃]Only oligomer structures are formed when coordinated with metal ions (Cu, Mn) having weaker binding ability. The synthesis of these structures reveals new strategies and methods for constructing novel three-dimensional supramolecular structures, and can also be used as model systems for studying the self-assembly behavior of three-dimensional structures.

Description

3D supramolecular material with various coordination configurations and preparation method and application thereof

Technical Field

The invention relates to the field of chemical synthesis, in particular to a 3D supramolecular material with various coordination configurations and a preparation method and application thereof.

Background

The fabrication of complex discrete supramolecular structures, particularly three-dimensional supramolecular cages, from simple molecular building blocks has attracted a wide range of interest to chemists not only because of their structural abundance, but also because of their wide range of applications in molecular recognition, sensing and supramolecular catalysis. Based on the dynamic and reversible properties of metal coordination bonds, the structure of supramolecular self-assembly is determined by two main factors, the first is the property of a building module such as metal ions and ligands, the second is external conditions such as concentration, solvent, anion, light and the like, the ligands and the metal ions are the most important factors in the process of building supramolecules, the influence of ligand design and external factors including the concentration solvent and the like on the supramolecular configuration is greatly researched, the influence of metals with different coordination binding capacities on the formation of supramolecules in the assembly process is only researched, and a system that the same ligand forms different supramolecular structures when being coordinated with different metals is urgently needed to be built. 2,2':6', 2' -Terpyridine (TPY) is used as a common tridentate ligand, can coordinate with different transition metal ions, and the coordination binding capacity is increased according to the sequence that Mn < Cu < Cd < Zn < Co, so the diversity of the coordination capacity between the terpyridine and the transition metal ions is fully utilized, and the influence of the transition metals with different binding capacities on the metal-organic supermolecular cage structure during coordination is researched.

Disclosure of Invention

The invention aims to provide a plurality of 3D supramolecular materials with various coordination configurations formed by coordinating a unified ligand with different transition metals and a preparation method thereof, and solves the problem of influence of coordination binding capacity of different transition metals on the formed supramolecular configuration in the prior art by improving material structures and processes.

The purpose of the invention is realized by adopting the following technical scheme:

in a first aspect, the present invention provides a 3D supramolecular material with multiple coordination configurations, wherein the supramolecular material comprises a unit structure represented by formula (i), and the supramolecular material is prismatic;

wherein M is a transition metal ion.

Preferably, M is bivalent or trivalent metal ions, and the bivalent or trivalent metal ions can be assembled with the four-arm terpyridine metal organic ligand to form metal organic supramolecules, and the stability is good. Further preferably, M is Fe² ⁺、Co³⁺、Os³⁺、Hg²⁺、Ir²⁺、Pd²⁺、Rh³⁺、Zn²⁺、Cu²⁺、Cd²⁺、Mn²⁺、Ni²⁺、Ru²⁺Or Mg²⁺At least one of (1).

In a second aspect, the present invention provides a method for preparing a 3D supramolecular material with multiple coordination configurations, comprising the steps of:

(1) preparing a four-arm terpyridine metal organic ligand shown in a formula (II):

(2) and (2) adding a solvent into the four-arm terpyridine metal organic ligand shown in the formula (II) prepared in the step (1), dissolving, then dropwise adding a metal salt solution, heating for reaction, adding an anion displacer after the reaction is finished, and filtering to obtain a precipitate, namely the supramolecular material.

The terpyridine metal organic ligand used in the step (2) is a four-arm ligand, has a unique geometric angle and configuration, and can be spontaneously assembled into a structurally precise, ordered and unique triangular prism or quadrangular prism structure with different divalent metal ions in a solution system.

Preferably, in the metal salt of step (2), the cation is Fe²⁺、Co³⁺、Os³⁺、Hg²⁺、Ir²⁺、Pd²⁺、Rh³⁺、Zn²⁺、Cu²⁺、Cd²⁺、Mn²⁺、Ni²⁺、Ru²⁺Or Mg²⁺At least one of; the anion being Cl^-Or NTf₂ ^-。

Preferably, the anion displacer in step (2) is selected from one of ammonium hexafluorophosphate or lithium bistrifluoromethanesulfonylimide. Displacement of Cl introduced during assembly by means of said anionic displacer^-Or NTf₂ ^-And under the action of ammonium hexafluorophosphate or lithium bistrifluoromethanesulfonimide, the supramolecular material can be separated out from the solvent better, and the separation and purification of subsequent precipitates are facilitated.

Preferably, the solvent in step (2) is at least one of alcohol, chloroform or ether.

More preferably, the solvent in step (2) is an alcohol and chlorine.

More preferably, in the step (2), the solvent is a mixed solution of methanol and chloroform, and the volume ratio of the methanol to the chloroform is 1: (1-1.5). The mixed solvent of methanol and chloroform plays an important role in forming the supramolecular material, the four-arm terpyridine ligand has good solubility in the mixed solvent of chloroform and methanol, and the generated supramolecular material can be well dissolved in acetonitrile.

Preferably, the heating reaction in the step (2) is carried out at the temperature of 40-70 ℃ for 5-10 h.

More preferably, the heating reaction in the step (2) is carried out at the temperature of 45-55 ℃ for 6-10 h.

Preferably, the preparation method of the four-arm terpyridine organic ligand shown in the formula (II) in the step (1) comprises the following steps:

(1) reacting 4-formylphenylboronic acid with 2-acetylpyridine under an alkaline condition to generate 4- (2, 2', 6, 2', -terpyridyl) -phenylboronic acid, namely an intermediate 1;

(2) carrying out substitution reaction on 2, 8-dibromo dibenzofuran and the intermediate 1 to obtain an intermediate 2;

(3) carrying out coordination reaction on the intermediate 1 and ruthenium trichloride hydrate to obtain an intermediate 3;

(4) 2, 6-dibromo-4-methoxyphenol reacts with 1, 8-diazabicycloundec-7-ene to obtain an intermediate 4;

(5) carrying out suzuki coupling reaction on the intermediate 4 and the intermediate 1 to obtain an intermediate 5;

(6) carrying out substitution reaction on the intermediate 5 and halogen to obtain an intermediate 6;

(7) coordinating the intermediate 3 with the intermediate 6 to obtain an intermediate 7;

(8) carrying out Suzuki-coupling reaction on the intermediate 7 and the intermediate 1 to obtain an X-type four-arm terpyridine metal organic ligand shown in a formula (II);

preferably, the halogen in step (6) is bromine.

The invention has the beneficial effects that:

(1) the 3D supramolecular material with various coordination configurations is constructed by self-assembly of the same four-arm terpyridine metal organic ligand and different transition metal ions through coordination bond guiding, and has a stable structure. When different transition metals are used for coordination, different structures can be obtained, wherein a metal with strong coordination capacity such as cobalt and zinc can obtain a quadrangular prism structure, a metal with weak coordination capacity such as cadmium can obtain a triangular prism structure, and a metal with weaker coordination capacity such as copper and manganese can only obtain a simple oligomer structure.

(2) The preparation method of the supermolecule material provided by the invention firstly synthesizes a four-arm metal organic ligand containing < tpy-Ru2+ -tpy > element by utilizing a step-by-step assembly strategy participated by Ru ions, different structures can be obtained when the supermolecule material is assembled with different metals, wherein a quadrangular prism structure is obtained when the supermolecule material is assembled with metal zinc and cobalt with strong coordination capacity, a triangular prism structure is obtained when the supermolecule material is coordinated with metal cadmium with weak coordination capacity, and only simple oligomer is obtained when the supermolecule material is coordinated with metal Mn and Cu with weaker coordination capacity.

(3) The supramolecular material provided by the invention is simple in preparation method, mild in reaction condition and beneficial to large-scale industrial production.

Drawings

The invention is further illustrated by means of the attached drawings, but the embodiments in the drawings do not constitute any limitation to the invention, and for a person skilled in the art, other drawings can be obtained on the basis of the following drawings without inventive effort.

FIG. 1 is a schematic structural diagram of supramolecular materials C1 and C2 prepared in example 2 of the present invention;

FIG. 2 is a schematic structural diagram of supramolecular material C3 obtained in example 2 of the present invention;

FIG. 3 is a flow chart for the preparation of ligand L in example 2 of the present invention;

FIG. 4 is a flow chart of the preparation of supramolecular material C1 according to example 2 of the present invention;

FIG. 5 is a flow chart of the preparation of supramolecular material C2 according to example 2 of the present invention;

FIG. 6 is a flow chart of the preparation of supramolecular material C3 according to example 2 of the present invention;

FIG. 7 shows the preparation of intermediate 2 obtained in example 2 of the present invention¹H NMR spectrum;

FIG. 8 shows the preparation of intermediate 4 obtained in example 2 of the present invention¹H NMR spectrum;

FIG. 9 shows intermediate 5 obtained in example 2 of the present invention¹H NMR spectrum;

FIG. 10 shows the preparation of intermediate 6 obtained in example 2 of the present invention¹H NMR spectrum;

FIG. 11 shows intermediate 7 obtained in example 2 of the present invention¹H NMR spectrum;

FIG. 12 shows ligand L prepared in example 2 of the present invention¹H NMR spectrum;

FIG. 13 is a mass spectrum of supramolecular material C1 obtained in example 2 of the present invention;

FIG. 14 is a mass spectrum of supramolecular material C1 obtained in example 2 of the present invention;

FIG. 15 is a mass spectrum of supramolecular material C1 obtained in example 2 of the present invention;

FIG. 16 shows the supramolecular material C1 obtained in example 2 of the present invention¹H NMR spectrum;

FIG. 17 is a diagram of supramolecular material C3 produced in example 2 of the present invention¹H NMR spectrum;

FIG. 18 is a TEM image of supramolecular material C1 obtained in example 2 according to the invention;

FIG. 19 is a TEM image of supramolecular material C2 obtained in example 2 according to the invention;

FIG. 20 is a TEM image of supramolecular material C3 obtained in example 2 according to the invention;

FIG. 21 is an AFM of supramolecular material C1 produced in example 2 of the present invention;

FIG. 22 is an AFM of supramolecular material C1 produced in example 2 of the present invention;

FIG. 23 is an AFM of supramolecular material C1 produced in example 2 of the present invention;

FIG. 24 is a fluorescence spectrum of organometallic ligands and supramolecules produced in example 2 of the invention;

FIG. 25 is a schematic diagram of different transition metals coordinated to form supramolecular materials prepared in example 2 of the present invention.

Detailed Description

For the purpose of more clearly illustrating the present invention and more clearly understanding the technical features, objects and advantages of the present invention, the technical solutions of the present invention will now be described in detail below, but are not to be construed as limiting the implementable scope of the present invention.

The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.

The invention is further described with reference to the following examples.

Example 1

A3D supramolecular material with multiple coordination configurations, ligands have different configurations when being assembled with different transition metals, the supramolecular material comprises a unit structure shown in a structural formula (I), and the supramolecular material is prismatic;

wherein M is a transition metal ion; ru is metallic ruthenium.

The transition metal ion M is Fe²⁺、Co³⁺、Os³⁺、Hg²⁺、Ir²⁺、Pd²⁺、Rh³⁺、Zn²⁺、Cu²⁺、Cd²⁺、Mn²⁺、Ni² ⁺、Ru²⁺、Mg²⁺At least one of (1).

Wherein M is a transition metal ion.

PreferablyAnd M is divalent or trivalent metal ions, and the divalent or trivalent metal ions can be assembled with the four-arm terpyridine metal organic ligand to form metal organic supramolecules, and the stability is good. Further preferably, M is Fe² ⁺、Co³⁺、Os³⁺、Hg²⁺、Ir²⁺、Pd²⁺、Rh³⁺、Zn²⁺、Cu²⁺、Cd²⁺、Mn²⁺、Ni²⁺、Ru²⁺Or Mg²⁺At least one of (1).

A preparation method of the 3D supramolecular material with multiple coordination configurations comprises the following steps:

The terpyridine metal organic ligand used in the step (2) is a four-arm ligand, has a unique geometric angle and configuration, and can be spontaneously assembled into a triangular prism or quadrangular prism structure with a precise, ordered and unique structure with different divalent metal ions in a solution system.

In the metal salt in the step (2), the cation is Fe²⁺、Co³⁺、Os³⁺、Hg²⁺、Ir²⁺、Pd²⁺、Rh³⁺、Zn²⁺、Cu²⁺、Cd²⁺、Mn²⁺、Ni²⁺、Ru²⁺Or Mg²⁺At least one of; the anion being Cl^-Or NTf₂ ^-。

In the step (2), the anion displacer is selected from one of ammonium hexafluorophosphate or lithium bis (trifluoromethanesulfonyl) imide. Using said anionic displacerBy exchanging Cl introduced during assembly^-Or NTf₂ ^-And under the action of ammonium hexafluorophosphate or lithium bistrifluoromethanesulfonimide, the supramolecular material can be separated out from the solvent better, and the separation and purification of subsequent precipitates are facilitated.

In the step (2), the solvent is at least one of alcohol, chloroform or ether.

In the step (2), the solvent is alcohol and chlorine.

In the step (2), the solvent is a mixed solution of methanol and chloroform, and the volume ratio of the methanol to the chloroform is 1: (1-1.5). The mixed solvent of methanol and chloroform plays an important role in forming the supramolecular material, the four-arm terpyridine ligand has good solubility in the mixed solvent of chloroform and methanol, and the generated supramolecular material can be well dissolved in acetonitrile.

The heating reaction temperature in the step (2) is 40-70 ℃, and the reaction time is 5-10 h.

The heating reaction temperature in the step (2) is 45-55 ℃, and the reaction time is 6-10 h.

The preparation method of the four-arm terpyridine organic ligand shown in the formula (II) in the step (1) comprises the following steps:

in the step (6), the halogen is bromine.

Example 2

A3D supramolecular material with various coordination configurations is composed of a unit structure shown in a formula (III), and the supramolecular material is prismatic;

the preparation method of the supramolecular material comprises the following steps:

(1) preparation of 4- (2, 2', 6, 2', -terpyridyl) -phenylboronic acid (intermediate 1):

ethanol (200mL) was added to a 500mL round-bottom flask, followed by NaOH (9.6g, 240mmol) and dissolved with stirring. 4-formylphenylboronic acid (6.0g, 40mmol) and 2-acetylpyridine (10.6g, 88mmol) were added successively, the reaction was stirred at room temperature for 24 hours, and NH was added₃·H₂O (28%, 150mmol), and the reaction was heated under reflux for 20 h. The reaction was cooled to room temperature, filtered under suction, and the residue was washed with ice-cold isopropanol and chloroform to give a pale purple powder (11.96g, 84.7%).¹H NMR(500MHz,CD₃OD,300K,ppm):δ8.71–8.68(m,2H,tpy-H^3’,5’),8.68–8.62(m,4H,tpy-H^6,6”andtpy-H^3,3”),8.01(td,J＝7.7,1.8Hz,2H,tpy-H^4,4”),7.78(d,J＝7.8Hz,2H,Ph-H^j),7.73(d,J＝8.0Hz,2H,Ph-H^k),7.48(ddd,J＝7.5,4.8,1.1Hz,2H,tpy-H^5,5”).¹³CNMR(125MHz,CD₃OD,300K,ppm):δ157.46,156.84,153.10,149.87,138.57,135.29,134.99,125.75,125.11,122.82,119.40。

(2) Preparation of intermediate 2:

2, 8-dibromodibenzofuran (1.00g,3.07mmol), intermediate 1(1.19g,3.37mmol) and sodium carbonate (976mg,9.21mmol) were first added sequentially to a single-necked round-bottomed flask, followed by the addition of the catalyst bis-triphenylphosphine palladium dichloride (108mg,0.154mmol), followed by 50mL of toluene and then by sonication, followed by the addition of 15mL of t-butanol, 30mL of distilled water, t-butanol asThe phase transfer agent enables the reaction to proceed better. After the solvent and the reactants were added, the whole reaction system was evacuated and purged with nitrogen 3 times, heated to 80 ℃ and stirred for 8 hours. After the reaction was completed and cooled to room temperature, extraction was performed with dichloromethane and saturated brine, and anhydrous NaSO was used₄Drying to remove residual water, removing solvent under reduced pressure to obtain crude product, separating by silica gel column chromatography, and purifying with CH₂Cl₂: the product was obtained in MeOH (100:0.75, v/v) with polarity and collected and the solvent was removed to yield 1.27g of a white solid (75% yield);¹H NMR(600MHz,CDCl₃,300K)δ8.82(s,2H,Tpy-H³'_, ⁵'),8.76(d,J＝5.5Hz,2H,Tpy-^6,6”),8.70(d,J＝7.9Hz,2H,Tpy-H^3,3”),8.17(d,J＝6.6Hz,2H,Ph-H^b),8.05(d,J＝8.3Hz,2H,Ph-H^f,g),7.90(t,J＝7.7Hz,2H,Tpy-H^4,4”),7.80(d,J＝8.4Hz,2H,Ph-H^a),7.79–7.77(m,1H,Ph-H^d),7.65(d,J＝8.5Hz,1H,Ph-H^e),7.58(d,J＝8.7Hz,1H,Ph-H^h),7.48(d,J＝8.7Hz,1H,Ph-H^c),7.40–7.35(m,2H,Tpy-H^5,5”)；¹³CNMR(126MHz,CDCl₃,300K)δ156.32,156.03,149.81,149.21,137.13,129.07,128.14–127.66,127.4,127.27,123.92,123.69–123.63,121.58,119.12,118.85。

(3) preparation of intermediate 3:

intermediate 2(415.5mg,0.75mmol) was weighed into a 200mL single-neck flask, 80mL chloroform was added and dissolved completely by sonication, and the weighed RuCl was added₃·H₂O (504.5mg,2.25mmol) was transferred to the flask, 80mL of methanol was measured in a measuring cylinder and poured into the flask and sonicated again to uniformly disperse the ruthenium trichloride hydrate in the solution, and heated under reflux at 65 ℃ for 24 hours. After the reaction was completed, the reaction mixture was allowed to stand to cool to room temperature, and then the solvent was removed. Transferring the obtained solid into a centrifuge tube, adding methanol, shaking and centrifuging, pouring out supernatant liquid and leaving solidThe above procedure was repeated by adding distilled water to give 485mg of a dark brown solid (85% yield).

(4) Preparation of intermediate 4:

2, 6-dibromo-4-methoxyphenol (5.20g,18.4mmol) was charged in a 100mL single-neck round-bottom flask, 50mL of acetone was poured in a graduated cylinder, and the mixture was ultrasonically dissolved sufficiently, and then 1, 8-diazabicycloundecen-7-ene (13.8mL,92.2mmol) was added dropwise to the flask and stirred at room temperature for 30 min. After the reaction is finished, adding 2mol/L HCL solution for neutralization, extracting with diethyl ether after the solution becomes clear, collecting an organic phase, and removing the solvent under reduced pressure to obtain a crude product. The obtained product was subjected to column chromatography using petroleum ether as an eluent to finally obtain 3.96g of white crystals (yield 73%).¹H NMR(400MHz,CDCl₃,300K)δ7.05(s,2H,Ph-H^c),3.83(s,3H,-OCH₃-H^a),3.76(s,3H,-OCH₃-H^b)；¹³CNMR(101MHz,CDCl₃,300K)δ156.42,148.11,118.26,117.92,60.82,56.03。

(5) Preparation of intermediate 5:

to a 250mL three-necked round bottom flask was added in sequence intermediate 4(440.8mg,1.5mmol), intermediate 1(1.59g,4.5mmol), sodium carbonate (954mg,9mmol), then 60mL of toluene was added to the reaction and sonicated to ensure that all was well dissolved, then 25mL of t-butanol, 10mL of distilled water were added, and after all the solution had been added, Pd (PPh) was added₃)₂Cl₂(105mg,0.15mmol,) as catalyst. Then the whole system is sealed, vacuumized, nitrogen-exchanged, pumped and discharged for 3 times, and reacted for 48 hours at 85 ℃. Cooling to room temperature, removing solvent under reduced pressure, adding 40mL methanol, ultrasonic treating under reflux for 30min, and filtering the mixture with suction filter funnelFiltering with CHCl₃As a benign solvent, MeOH was recrystallized as a poor solvent to finally obtain 880mg of a white solid (yield 78%).¹H NMR(400MHz,CDCl₃,300K)δ8.82(s,4H,Tpy-H^3',5'),8.75(d,J＝5.6Hz,4H,Tpy-H^6,6”),8.70(d,J＝7.9Hz,4H,Tpy-H^3,3”),8.01(d,J＝8.4Hz,4H,Ph-H^J),7.89(t,J＝7.7Hz,4H,Tpy-H^4,4”),7.81(d,J＝8.4Hz,4H,Ph-H^k),7.39–7.33(t,4H,Tpy-H^5,5”),6.99(s,2H,Ph-H^c),3.91(s,3H,-OCH₃-H^a),3.19(s,3H,-OCH₃-H^b)；¹³CNMR(101MHz,CDCl₃,300K)δ156.42,155.86,150.08,149.06,139.41,137.41,137.05,136.02,129.92,127.28,123.93,121.48,118.97,115.50,60.83,55.87。

(6) Preparation of intermediate 6:

intermediate 5(400mg,0.53mmol) was weighed on an electronic balance and added to a 100mL single-neck flask, 30mL chloroform was added thereto and dissolved completely by sonication, and then 15mL HCl solution was added dropwise to the flask via a constant pressure dropping funnel₃Br of₂(4mL), after dropping slowly, a condenser was added and the reaction was refluxed at 80 ℃ for 48 hours. Standing after the reaction is finished to cool the reaction product to room temperature, directly filtering, transferring the obtained filter residue into a saturated sodium sulfite solution to be uniformly dispersed by ultrasonic treatment, and simultaneously adding saturated Na into the filtrate₂SO₃Solution, quenching excess bromine. The obtained residue dispersed in the solution was extracted with DCM and saturated brine, the organic phase was collected and dried over anhydrous magnesium sulfate to remove residual water, and the organic phase was concentrated to 5mL, and then recrystallized by adding methanol which is a poor solvent, to which was added, to obtain 310mg of pale purple powder (yield: 64%) after suction filtration.¹H NMR(400MHz,CDCl₃)δ8.81(s,4H,Tpy-H^3',5'),8.74(d,J＝5.6Hz,4H,Tpy-H^6,6”),8.69(d,J＝7.9Hz,4H,Tpy-H^3,3”),8.00(d,J＝8.3Hz,4H,Ph-H^b),7.89(t,J＝7.7Hz,4H,Tpy-H^4,4”),7.53(d,J＝8.3Hz,4H,Ph-H^a),7.39–7.34(t,4H,Tpy-H^5,5”),3.99(s,3H,-OCH₃-H^d),3.06(s,3H,-OCH₃-H^e)；¹³C NMR(101MHz,CDCl₃)δ156.22,155.99,150.08,149.18,138.19,137.61,137.07,130.59,127.19,123.94,121.43,119.50,119.12,77.33,77.07,76.75,61.00,60.60。

(7) Preparation of intermediate 7:

intermediate 6(200mg,0.22mmol) was first weighed into a 250mL single neck round bottom flask, dissolved by sonication in 50mL chloroform solution, then weighed intermediate 3(502mg,0.66mmol) was added, 60mL methanol was weighed in a graduated cylinder and poured into the flask, mixed well, then 500 μ LN-ethylmorpholine was added dropwise to the reaction using a pipette, and heated at 65 ℃ under reflux for 48 hours. After the reaction was completed, the solvent was removed under reduced pressure, and then a small amount of CHCl was added₃Dissolving the crude product, adding neutral alumina powder, removing solvent to obtain dry sample, separating by column chromatography, removing impurities with small polarity proportion, and removing impurities in CH₂Cl₂The product was collected in MeOH (100: 1.75, v/v) with polarity and dried by spinning to give 420mg of red powder (30% yield).¹H NMR(400MHz,CD₃OD,300K)δ9.40(d,J＝6.5Hz,8H,Tpy-H^A ^,B3’5’),8.95(dd,J＝7.8,4.1Hz,8H,Tpy-H^A,B3,3”),8.54(s,2H,Ph-H^c),8.47(d,J＝8.1Hz,8H,Ph-H^A,Ba),8.40(d,J＝1.9Hz,2H,Ph-H^d),8.16(d,J＝8.3Hz,4H,Ph-H^Ab),8.05(dd,J＝13.8,5.9Hz,10H,Tpy-H^A,B4,4”,Ph-H^e),7.84–7.78(m,6H,Ph-H^Bb,Ph-H^f),7.69(dd,J＝8.7,2.0Hz,2H,Ph-H^h),7.64–7.59(m,10H,Tpy-H^A,B6,6”,Ph-H^g),7.33–7.29(m,8H,Tpy-H^A,B5,5”),4.06(d,J＝19.9Hz,6H,-OCH₃-H^m,n)。

(8) Preparing a final metal-organic ligand L represented by formula (IV):

firstly weighing compound K7(100mg,0.042mmol) in a 100mL single-neck round-bottom flask, adding 30mL acetonitrile into the flask and carrying out ultrasonic treatment to ensure that the compound K7 is completely dissolved, then adding 4-terpyridyl phenylboronic acid (179mg,0.508mmol) and potassium carbonate (70.2mg,0.508mmol), then measuring 30mL methanol by using a measuring cylinder, pouring the methanol into the flask, and quickly adding tetratriphenylphosphine palladium (39mg,0.034mmol) to ensure that the compound K7 is not oxidized so as to exert the catalytic action to the maximum extent; the whole system is subjected to the operation of removing oxygen and replacing nitrogen, and the operation is repeated for three times to ensure that the reaction is carried out under the anaerobic condition. Heating at 80 ℃ for four days to carry out Suzuki coupling reaction, carrying out suction filtration on the obtained reaction liquid by using kieselguhr after the reaction is finished, and cleaning the residual product of the kieselguhr by using acetonitrile. The obtained filtrate was concentrated, and LiNTf was added thereto₂The product was precipitated and purified by recrystallization from evaporated solvent, repeated twice and filtered again, and the red solid obtained was dried to yield 55mg of red solid (41% yield).¹H NMR(400MHz,CD₃CN,300K)δ9.11(s,4H,Tpy-H^A3’5’),9.03(s,4H,Tpy-H^B3’5’),8.87(s,4H,Tpy-H^C3’5’),8.80(s,4H,Tpy-H^D3’5’),8.79–8.75(m,8H,Tpy-H^A,B3,3”),,8.69(d,J＝8.4Hz,12H,Tpy-H^C,D3,3”,Ph-H^c.d),8.63(d,J＝7.7Hz,8H,Tpy-H^C ^,D6,6”),8.39(d,J＝8.4Hz,4H,Tpy-H^Aa),8.21(d,J＝3.6Hz,8H,Tpy-H^Ba,Ab),8.11(d,J＝8.4Hz,2H,Ph-H^e),8.02(d,J＝8.1Hz,8H,Tpy-H^Ca,Da),7.98(d,J＝8.0Hz,8H,Tpy-H^A,B3,3”),7.93(dd,J＝8.5,5.4Hz,16H,Tpy-H^{C,D4,4”,C,D6,6”}),7.87–7.82(m,4H,Ph-H^f,h),7.77(d,J＝8.4Hz,4H,Tpy-H^Ba),7.65(s,2H,H^g),7.51–7.47(m,8H,Tpy-H^Cb,Db),7.44–7.41(m,8H,Tpy-H^C,D5,5”),7.19–7.13(m,9H,Tpy-H^A,B5,5”),3.22(s,3H,-OCH₃-H^m),3.16(s,3H,-OCH₃-Hⁿ)。

(9) Preparation of supramolecular materials (denoted supramolecular materials C1, C2, C3) consisting of a unit structure represented by formula (III):

c1 Final ligand L (10mg, 2.34. mu. mol) was dissolved in 12mLCH₃CN solution, Zn (NTf) is added₂)₂(2.94mg, 4.68. mu. mol) in MeOH; the mixture was then stirred at 60 ℃ for 8 hours. Adding dissolved LiNTf₂In MeOH, a large amount of red flocculent precipitate appeared immediately, centrifuged, and the residue was washed three times with distilled water and dried under vacuum to give a red powdery solid (11.3mg, 98%).

Of supramolecular material C1¹The H NMR data are as follows:¹H NMR(400MHz,CD₃CN,300K)δ9.17–9.06(br,8H,Tpy-H^{A,B,C,D3’5’}),8.80–8.74(br,J＝22.4Hz,10H,Tpy-H^{A,B,C,D3,3”},Ph-H^c.d),8.47–8.39(br,4H,Tpy-H^A,B4,4”),8.35–8.30(br,4H,Tpy-H^Ca,Da),8.26–8.18(br,8H,Tpy-H^A,B6,6”,Tpy-H^Cb,Db,Aa,Ba),8.12–8.09(br,2H,Ph-H^e),8.01–7.85(br,J＝33.7Hz,14H,Tpy-H^{A,B6,6”,C,D4,4”},Ph-H^h),7.52–7.38(br,J＝4.2Hz,10H,Tpy-H^{A,B5,5”,C,D6,6”},Ph-H^g),7.25–7.16(br,4H,Tpy-H^C,D5,5”),3.45(d,J＝7.0Hz,3H,-OCH₃-H^m,n)。

c2 Final ligand L (8mg, 1.87. mu. mol) was dissolved in 12mLCH₃Adding CoCl into CN solution₂·6H₂A solution of O (0.89mg,3.76 μmol) in MeOH; the mixture was then stirred at 60 ℃ for 8 hours. Adding LiNTf dissolved therein₂The MeOH solution is subjected to anion conversion, a large amount of red flocculent precipitate appears immediately, centrifugal separation is carried out, filter residue is washed with distilled water for three times, and red powdery solid is obtained after vacuum drying(7.8mg，98％)。

C3 Final ligand L (9mg, 2.11. mu. mol) was dissolved in 12mLCH₃Adding Cd (NO) into CN solution₃)₂·4H₂A solution of O (1.3mg, 4.22. mu. mol) in MeOH; the mixture was then stirred at 60 ℃ for 8 hours. Adding dissolved LiNTf₂In MeOH, a large amount of red flocculent precipitate appeared immediately, centrifuged, and the residue was washed three times with distilled water and dried under vacuum to give a red powdery solid (9.5mg, 98%).

Of supramolecular material C3¹The H NMR data are as follows:¹H NMR(400MHz,CD₃CN,300K)δ9.17–9.02(br,J＝29.5Hz,8H,Tpy-H^{A,B,C,D3’5’}),8.82–8.66(br,10H,Tpy-H^{A,B,C,D3,3”},Ph-H^c.d),8.41–8.16(br,J＝80.4Hz,17H,Tpy-H^{A,B4,4”,A,B5,5”},Tpy-H^Aa,Ba,Cb,Db,Ph-H^e),8.02–7.83(br,13H,Tpy-H^C ^,D4,4”,Ph-H^Ab.Bb,Ca,Da,Ph-H^h),7.51–7.41(br,9H,Tpy-H^A,B5,5”,Tpy-H^C,D6,6”,Ph-H^g),7.24–7.17(br,4H,Tpy-H^C,D5,5”),3.27(s,3H,-OCH₃-H^m,n).

the structure of supramolecular material C1, C2 and C3 is schematically shown in figure 1 and figure 2, and the preparation process is shown in figure 3.

And (4) detecting a result:

(1) characterizing discrete supramolecular self-assembly using multi-dimensional mass spectrometry:

electrospray ionization mass spectrometry (ESI-MS) is a method for detecting the molecular weight of a sample component by measuring the mass-to-charge ratio (m/z) of the sample component, can generate multiple charge peaks for the determination of a high molecular compound, enlarges the molecular mass range of detection compared with the conventional mass spectrometry, simultaneously improves the sensitivity of an instrument, and can reach 0.005% precision when the resolution is 1000 in the detection of samples with the order of pmol or less. ESI-MS is a soft ionization mode, which does not produce fragments of sample molecules under a certain voltage, and is the first method for detecting and analyzing relatively pure macromolecular compounds.

Firstly, the supermolecular material C1 is characterized by using electrospray ionization mass spectrometry (ESI-MS), the molecular weight and the composition of the supermolecular material are measured, and the signal peak of the supermolecular material C1 is ESI-TOF (M/z):1555.65[ M-12 NTf)₂-]¹²⁺(calcdm/z:1555.65),1414.44[M-13NTf₂-]¹³⁺(calcdm/z:1414.44),1293.40[M-14NTf₂-]¹⁴⁺(calcdm/z:1293.40),1188.49[M-15NTf₂-]¹⁵⁺(calcdm/z:1188.49),1096.71[M-16NTf₂-]¹⁶⁺(calcdm/z:1096.71),1015.72[M-17NTf₂-]¹⁷⁺(calcdm/z:1015.72),943.73[M-18NTf₂-]¹⁸⁺(calcdm/z:943.73),879.31[M-19NTf₂-]¹⁹⁺(calcdm/z: 879.31); the molecular weight of the supramolecular material C1 is 22029Da calculated according to data, and the calculation value is matched with the theoretical calculation value.

And then, detecting whether isomers or other conceived isomers exist in the supramolecular material by using TWIM-MS. The results of supramolecular material C1 were found to show that the charge numbers from 10+ to 24+ are a set of sharp, narrow and separated single-set signal peaks, thus demonstrating no other isomerism in the system and a single structural configuration.

The supramolecular material C2 is characterized by using an electrospray ionization mass spectrum (ESI-MS), the molecular weight and the composition of the supramolecular material are measured, and the signal peak of the supramolecular material C2 is 1989.75[ M-11 NTf)₂-]¹¹⁺(calcdm/z:1989.75)1551.36[M-12NTf₂-]¹²⁺(calcdm/z:1551.36),1410.47[M-13NTf₂-]¹³⁺(calcdm/z:1410.47),1289.71[M-14NTf₂-]¹⁴⁺(calcdm/z:1289.71),1185.06[M-15NTf₂-]¹⁵⁺(calcdm/z:1185.06),1093.48[M-16NTf₂-]¹⁶⁺(calcdm/z:1093.48),1012.68[M-17NTf₂-]¹⁷⁺(calcdm/z:1012.68),940.86[M-18NTf₂-]¹⁸⁺(calcdm/z:940.86),876.60[M-19NTf₂-]¹⁹⁺(calcdm/z:876.60)。

The molecular weight of the supramolecular material C2 is calculated to be 21978Da according to data, and the calculation is matched with the theoretical calculation value.

The TWIM-MS results of the supramolecular material C2 show that the charge numbers from 10+ to 24+ are a set of sharp, narrow and separated single-set signal peaks, thus demonstrating no other isomers in the system and a single structural configuration.

The supramolecular material C3 is characterized by using an electrospray ionization mass spectrum (ESI-MS), the molecular weight and the composition of the supramolecular material are measured, and the signal peak of the supramolecular material C3 is 1400.29[ M-10NTf ]₂-]¹⁰⁺(calcdm/z:1400.29),1247.53[M-11NTf₂-]¹¹⁺(calcdm/z:1247.53),1120.22[M-12NTf₂-]¹²⁺(calcdm/z:1120.22),1012.50[M-13NTf₂-]¹³⁺(calcdm/z:1012.50),920.17[M-14NTf₂-]¹⁴⁺(calcdm/z:920.17),840.15[M-15NTf₂-]¹⁵⁺(calcdm/z:840.15),770.13[M-16NTf₂-]¹⁶⁺(calcdm/z:770.13),708.35[M-17NTf₂-]¹⁷⁺(calcdm/z: 708.35); the molecular weight of the supramolecular material C3 is 16804Da calculated according to the data, and the calculated value is matched with the theoretical calculation value.

The TWIM-MS results of the supramolecular material C3 show that the charge numbers from 8+ to 18+ are a set of sharp, narrow and separated single-group signal peaks, thus demonstrating no other isomers in the system and single structural configuration.

(2) Characterization of the surface appearance of the supramolecular material:

a Transmission Electron Microscope (TEM) is an electron optical instrument with high resolution and high magnification, which uses an electron beam with an extremely short wavelength as a light source and uses an electromagnetic lens to focus and image the transmission electron. The TEM is a testing means capable of directly observing the microscopic morphology, and the TEM is used for representing the surface morphology of the cage-shaped supermolecule. Respectively dissolving supramolecular materials C1, C2 and C3 in acetonitrile solution to obtain solution with concentration of 5 × 10^-6And (3) uniformly dispersing the solution in the acetonitrile solution by ultrasonic treatment for two minutes in mol/L, and using an ultrathin carbon supporting film as a substrate.

FIG. 15 is a TEM image of supramolecular material C1, and it can be seen from FIG. 15 that supramolecular material C1 is a series of uniformly distributed cage-like supramolecular materials with a diameter of about 6.4nm, which is consistent with the diameter size of the molecular structure simulated by software.

FIG. 16 is a TEM image of supramolecular material C2, and it can be seen from FIG. 16 that supramolecular material C1 is a series of uniformly distributed cage-like supramolecular materials with a diameter of about 6.5nm, which is consistent with the diameter size of the molecular structure simulated by software.

FIG. 17 is a TEM image of supramolecular material C3, and it can be seen from FIG. 17 that supramolecular material C2 is a series of uniformly distributed cage-like supramolecular materials with a diameter of about 4.1nm, which is consistent with the diameter size of the molecular structure simulated by software.

An atomic force microscope, a novel instrument with high atomic resolution, can detect the physical properties including the appearance of various materials and samples in a nanometer area in the atmosphere and liquid environment or directly carry out nanometer operation. Respectively dissolving supramolecular materials C1, C2 and C3 in acetonitrile solution to obtain solution with concentration of 5 × 10^-6The solution of mol/L is evenly dispersed in the acetonitrile solution by ultrasonic treatment for two minutes, and the solution is dripped on the surface of a mica sheet and then dried in the air.

FIG. 18 is a TEM image of supramolecular material C1, and it can be seen from FIG. 18 that supramolecular material C1 is a series of uniformly distributed cage-like supramolecular materials with a height of about 4.1nm, which is consistent with the diameter size of the molecular structure simulated by software.

FIG. 19 is a TEM image of supramolecular material C2, and it can be seen from FIG. 19 that supramolecular material C1 is a series of uniformly distributed cage-like supramolecular materials with a height of about 4.2nm, which is consistent with the diameter size of the molecular structure simulated by software.

FIG. 20 is a TEM image of supramolecular material C3, and it can be seen from FIG. 20 that supramolecular material C2 is a series of uniformly distributed cage-like supramolecular materials with a height of about 4.1nm, which is consistent with the diameter size of the molecular structure simulated by software.

(3) Determining the photophysical properties of the ligand L and the supramolecular materials C1, C2 and C3:

the light emission spectroscopy measures the spectral properties of the organic ligands and supramolecular materials. Dissolving ligand L in acetonitrile solution with the concentration of 10^-6mol/L; respectively dissolving supramolecular materials C1, C2 and C3 in acetonitrile solution at a concentrationIs 10^-6mol/L, an excitation wavelength of 385nm, and measurement at 73K gave a fluorescence emission spectrum as shown in FIG. 21.

The invention provides a construction method of a supermolecule system with different configurations by using the same ligand and different transition metal coordination. The invention firstly utilizes the characteristic of high stability of metallic ruthenium to synthesize a novel ruthenium-containing catalyst<tpy-Ru² ⁺-tpy>When the four-arm metal organic ligand L is assembled with transition metals with different coordination strengths, different three-dimensional metal organic supermolecular configurations are formed. Wherein the use of metal ions (Co, Zn) with strong ligand binding capacity facilitates the formation of larger structures [ M₈L₄]Whereas metal ions (Cd) with weak ligand binding capacity lead to the formation of smaller structures [ M [₆L₃]Only oligomer structures are formed when coordinated with metal ions (Cu, Mn) having weaker binding ability. The synthesis of these structures reveals new strategies and methods for constructing novel three-dimensional supramolecular structures, and can also be used as model systems for studying the self-assembly behavior of three-dimensional structures.

Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims

1. 3D supramolecular material with various coordination configurations, characterized in that it has different configurations when assembled with different transition metals using the same ligand, said supramolecular material comprising a unit structure according to formula (i), said supramolecular material being prismatic;

wherein M is a transition metal ion; ru is metallic ruthenium.

2. 3D supramolecular material with multiple coordination configurations as claimed in claim 1, characterized in that said transition metal ion M is Fe²⁺、Co³⁺、Os³⁺、Hg²⁺、Ir²⁺、Pd²⁺、Rh³⁺、Zn²⁺、Cu²⁺、Cd²⁺、Mn²⁺、Ni²⁺、Ru²⁺、Mg²⁺At least one of (1).

3. A method for preparing 3D supramolecular materials with various coordination configurations as claimed in any one of claims 1 to 2, characterized in that it comprises the following steps:

(1) preparation of a compound of formula (II)<tpy-Ru²⁺-tpy>A four-arm terpyridine metal organic ligand of a motif;

4. The method for preparing 3D supramolecular materials with multiple coordination configurations as claimed in claim 3, wherein said anion exchanger in step (2) is selected from at least one of ammonium hexafluorophosphate and lithium bis (trifluoromethanesulfonylimide).

5. The method for preparing 3D supramolecular materials with multiple coordination configurations as claimed in claim 3, wherein the solvent in step (2) is at least one of alcohol, chloroform, and ether.

6. The method for preparing 3D supramolecular materials with various coordination configurations as claimed in claim 5, wherein said solvent is a mixed solution of methanol and chloroform, volume ratio of methanol to chloroform is 1: (1-1.5).

7. The method for preparing 3D supramolecular materials with multiple coordination configurations as claimed in claim 3, wherein the temperature of heating reaction in step (2) is 40-70 ℃ and reaction time is 5-10 h.

8. The method for preparing 3D supramolecular materials with multiple coordination configurations as claimed in claim 7, wherein the temperature of heating reaction in step (2) is 45-55 ℃ and reaction time is 6-10 h.

9. The method for preparing 3D supramolecular materials with various coordination configurations as claimed in claim 3, wherein the method for preparing the four-arm terpyridine organic ligand represented by formula (II) in step (1) comprises the following steps:

(8) and (3) carrying out Suzuki-coupling reaction on the intermediate 7 and the intermediate 1 to obtain the X-type four-arm terpyridine metal organic ligand shown in the formula (II).

10. The method for preparing 3D supramolecular materials with multiple coordination configurations as claimed in claim 9, wherein said halogen in step (6) is bromine.