An anthracene ring-based sandwich trinuclear cluster-based cubic cage complex and a synthesis method thereof

Abstract

The present application belongs to the technical field of complex synthesis, and particularly relates to a sandwiched three-nucleus cluster-based cubic cage complex based on anthracene ring and a synthesis method thereof. The present application takes 9,10-dibromoanthracene and imidazole as raw materials, first synthesizes a bidentate imidazole compound, then synthesizes a bidentate imidazole hexafluorophosphonium salt ligand, then synthesizes a bidentate organic thione ligand, and finally takes the bidentate organic thione ligand and a three-nucleus platinum cluster ([Tr2Pt3(CH3CN)3][X]2, X = BF4, PF6, NO3) as raw materials to synthesize the sandwiched three-nucleus cluster-based cubic cage complex based on anthracene ring. The present application constructs a series of sandwiched three-nucleus cluster-based cubic cage complexes by taking a three-nucleus cluster as a metal element and an anthracene ring linker as a bridging ligand, and the sandwiched three-nucleus cluster-based cubic cage complexes have the advantages of high yield and good stability, and different functional characteristics are determined according to different topological structures. The method enriches the supermolecular topological structure library and provides a train of thought for developing new functional materials.

Description

Technical Field

[0001] This invention belongs to the field of coordination compound synthesis technology, specifically relating to an anthracene-based sandwich trinuclear cluster cubic cage coordination compound and its synthesis method. Background Technology

[0002] Over the past few decades, the design and synthesis of discrete metal multinuclear nanostructures have attracted widespread attention, with various two-dimensional and three-dimensional structures reported. Coordination-driven self-assembly is one of the most effective strategies for constructing supramolecular metal coordination cages. Its core elements are the selection and design of metal motifs and ligand modules to ensure their polymerization direction. The selected precursor motifs must have a certain degree of rigidity, and their coordination sites must have a pre-defined angle. These building blocks typically have multiple coordination sites with angles ranging from 0 to 180°. The ligands acting as donors and the precursors providing the metal centers form coordination bonds in appropriate stoichiometric ratios, thereby forming structurally diverse cyclic molecules and discrete supramolecular complexes. Materials prepared with these structures can perform molecular recognition, adsorption, catalysis, drug delivery, and sensing, and are expected to be used as next-generation materials.

[0003] Organic ligands used as building blocks are generally selected from naphthalene, anthracene, pyrene, phenazine, and phenothiazine as linkers. Among them, anthracene has robust photophysical behavior and a plate-like molecular shape. Furthermore, different sites can be substituted to synthesize organic ligands with different angles and lengths. Therefore, it is widely used as a multifunctional structural unit for constructing attractive and functional molecules and molecular assemblies through covalent and non-covalent bonds. Additionally, the unique structure of anthracene ring molecules, which can undergo photochemical [4+4] cycloaddition and [4+2] oxygenation reactions, allows for the post-assembly modification of discrete metal-organic frameworks containing anthracene. Currently, a number of metal-organic supramolecular complexes have been constructed using mononuclear metal nodes and ligands. However, there are few reports on constructing functionalized supramolecular complexes using binuclear or multinuclear metal clusters instead of mononuclear metal ions as the metal central building blocks. Summary of the Invention

[0004] In view of the current situation where the coordination cage structure is relatively simple, the configuration is fixed, the stability is poor and the physicochemical properties are limited, and the coordination center is limited to metal ions and metal-oxygen clusters, the purpose of this invention is to provide an anthracene ring-based sandwich trinuclear cluster-based cubic cage complex and its synthesis method. Specifically, it is to construct a series of dye-adsorbable cubic cage supramolecular complexes with sandwich-type metal clusters as the coordination core and the synthesis method thereof.

[0005] The implementation process of this invention is as follows:

[0006] An anthracene ring-based sandwich trinuclear cluster-based cubic cage complex, the chemical structural formula of which is shown below:

[0007] ;

[0008] Where X is BF4 - PF6 - Or NO3 - Any one of them;

[0009] R is selected from straight-chain alkyl groups having 1-8 carbon atoms.

[0010] The above-described synthetic method for anthracene-based sandwich trinuclear cluster-based cubic cage complexes uses 9,10-dibromoanthracene and imidazole as starting materials. First, a bidentate imidazole compound is synthesized. Then, a bidentate imidazole hexafluorophosphate ligand is synthesized using the bidentate imidazole compound as a starting material. Next, a bidentate organothione ligand is synthesized using the bidentate imidazole hexafluorophosphate ligand as a starting material. Finally, the bidentate organothione ligand and a trinuclear platinum cluster ([Tr2Pt3(CH3CN)3][X]2, X=BF4) are used as starting materials. - PF6 - Or NO3 - Using anthracene rings as raw materials, sandwich trinuclear cluster-based cubic cage complexes were synthesized.

[0011] The above synthesis method includes the following steps:

[0012] (1) Synthesis of bidentate imidazole compounds

[0013] 9,10-dibromoanthracene, imidazole, K2CO3, and CuSO4·5H2O were added to a sealed container, and then heated to carry out a coupling reaction. After the reaction was completed, the product was washed, filtered, dried, and chromatographically purified to obtain a bidentate imidazole compound.

[0014] ;

[0015] (2) Synthesis of onium salt ligands of didentate imidazole hexafluorophosphate

[0016] The didentate imidazole compound obtained in step (1) was dissolved in DMF solution, and RBr was added and heated in the dark to react. After the reaction was completed, the mixture was concentrated by rotary evaporation, and then ethyl acetate was added to produce a precipitate. The precipitate was filtered and dissolved in methanol. Then, a methanol solution of ammonium hexafluorophosphate was added to produce a precipitate. The mixture was stirred overnight at room temperature in the dark. After the reaction was completed, the didentate imidazole hexafluorophosphate ligand was obtained by filtration. In RBr, R is a straight-chain alkyl group with 1-8 carbon atoms.

[0017] ;

[0018] (3) Synthesis of bidentate organothione ligands

[0019] The bidentate imidazole hexafluorophosphate salt ligands obtained in step (2) were dissolved in CH3CN, and sulfur powder and potassium carbonate were added. The mixture was then heated and stirred under reflux in the dark. After the reaction was completed, the bidentate organothione ligands were obtained by filtration and purification.

[0020] ;

[0021] (4) Synthesis of sandwich trinuclear cluster-based cubic cage complexes

[0022] Weigh out the trinuclear platinum cluster [Tr2Pt3(CH3CN)3][X]2 and dissolve it in acetonitrile; weigh out the bidentate organothione ligand obtained in step (3) and dissolve it in dichloromethane; add the acetonitrile solution of the trinuclear platinum cluster [Tr2Pt3(CH3CN)3][X]2 to the dichloromethane containing the bidentate organothione ligand, stir the reaction at room temperature in the dark, then centrifuge and concentrate the supernatant by rotary evaporation, then add diethyl ether to precipitate the precipitate, and filter to obtain the sandwich trinuclear cluster-based cubic cage complex; wherein X in [Tr2Pt3(CH3CN)3][X]2 is BF4. - PF6 - Or NO3 - Any one of them;

[0023] .

[0024] Furthermore, in step (1), the heating temperature for the heating coupling reaction is 180°C. o C~200 o C, the reaction time is 36h.

[0025] Furthermore, in step (1), the molar ratio of 9,10-dibromoanthracene, imidazole, K2CO3, and CuSO4·5H2O is 1.49:59.52:17.85:0.59.

[0026] Furthermore, in step (2), the heating temperature for the reaction in the dark is 110 °C and the reaction time is 24 h.

[0027] Furthermore, in step (2), the molar ratio of the didentate imidazole compound, RBr, and ammonium hexafluorophosphate is 0.64:5.12:5.12.

[0028] Furthermore, in step (3), the reaction time for heating, stirring, and refluxing in the dark is 48 hours; in step (4), the reaction time for stirring in the dark at room temperature is 12 hours.

[0029] Furthermore, in step (3), the molar ratio of the didentate imidazole hexafluorophosphate ligand, sulfur powder, and potassium carbonate is 0.34:1.36:1.36.

[0030] Furthermore, in step (4), the molar ratio of the trinuclear platinum cluster [Tr2Pt3(CH3CN)3][X]2 and the bidentate organothione ligand is 0.047:0.071.

[0031] The design concept of this invention: This invention designs a series of organothiophene ligands with anthracene rings as the base plate, and assembles them with trinuclear platinum metal clusters to obtain the first cubic cage complex constructed with sandwich-type metal cluster bases as metal nodes. This cubic cage complex can achieve the adsorption of dyes.

[0032] The positive effects of this invention are as follows: This invention constructs a series of sandwich trinuclear cluster-based cubic cage complexes using trinuclear clusters as metal units and anthracene ring linkers as bridging ligands. These complexes have advantages such as high yield and good stability. Different functional characteristics are determined by different topological structures. This method enriches the supramolecular topological structure library and provides ideas for the development of new functional materials. Attached Figure Description

[0033] Figure 1 The 9,10-diimidazole anthrathione ligand {[LR]} in Example 1 ; Single crystal structure diagram of (n=3)};

[0034] Figure 2 The sandwich-type trinuclear platinum cluster-based cubic cage complex {[C8(LR)} in Example 1 12 X 16 n=3, X=BF4 - The single-crystal structure diagram of};

[0035] Figure 3 The standard curve for methyl orange solution;

[0036] Figure 4 This is a graph showing the effect of the amount of the target product complex on the adsorption rate in Example 1;

[0037] Figure 5 The graph shows the change in UV absorption of methyl orange with the amount of the target product complex added in Example 1;

[0038] Figure 6 This is a graph showing the effect of adsorption time on adsorption rate.

[0039] Figure 7 The graph shows the change in UV absorption of methyl orange over adsorption time.

[0040] Figure 8 The graph shows the change in UV absorption of methyl orange with the initial dye concentration.

[0041] Figure 9 Langmuir adsorption isotherm;

[0042] Figure 10 The Freundlich adsorption isotherm. Detailed Implementation

[0043] The present invention will be further described below with reference to the embodiments.

[0044] Example 1 Sandwich Trinuclear Cluster-Based Cubic Cage Complex 1a

[0045] The method for synthesizing the sandwich trinuclear cluster-based cubic cage complex described in this embodiment specifically includes the following steps:

[0046] (1) Synthesis of 9,10-diimidazole anthracene:

[0047]

[0048] 9,10-Dibromoanthracene (500 mg, 1.49 mmol), imidazole (4.052 g, 59.52 mmol), K₂CO₃ (2.467 g, 17.85 mmol), and CuSO₄·5H₂O (148 mg, 0.59 mmol) were weighed and poured into a beaker. After stirring evenly, the mixture was poured into a vacuum reactor and placed in an oven at 180 °C for 36 h. After the reaction was complete, the mixture was washed with a large amount of water and filtered until the filtrate was colorless. The filter cake was dried in a vacuum drying oven at 75 °C, followed by column chromatography. The product was collected polarly using a dichloromethane:methanol eluent with a volume ratio of 30:1. 200 mg of a yellow solid powder was collected, yield: 43%. 1 H NMR (400 MHz, CDCl3): δ =7.83 (s, 2H), 7.54 (m, 8H), 7.49 (s, 2H), 7.33(s, 2H) ppm.

[0049] (2) 9,10-Diimidazole anthracene hexafluorophosphate salt {[AR](PF6)} 2; Composition of (n=3)}

[0050]

[0051] The 9,10-diimidazole anthracene (200 mg, 0.64 mmol) obtained in step (1) was added to a 50 mL Shrek tube, dissolved in 5 mL of DMF solution, and then bromobutane (702 mg, 5.12 mmol) was added dropwise. The mixture was heated to 110 °C in the dark for 24 h. A large amount of brown precipitate was produced during the reaction. After the reaction was completed, the mixture was concentrated by rotary evaporation, and a large amount of ethyl acetate was added. Immediately, a large amount of yellowish-brown precipitate was produced. The mixture was filtered, and the filter cake was dissolved in methanol. Then, 5 mL of methanol solution of ammonium hexafluorophosphate (835 mg, 5.12 mmol) was added. Immediately, a large amount of brownish-brown precipitate was produced. The mixture was stirred overnight at room temperature in the dark. After the reaction was completed, the mixture was filtered, and 252 mg of brownish-brown solid powder was collected. The filter cake was dried and 400 mg of yellowish-brown solid powder was collected. Yield: 83%. 1 H NMR (400 MHz, DMSO-d6): δ = 10.03 (d, 2H), 8.45 (s, 2H), 8.36 (t, 1H), 8.31 (t, 1H), 7.88 (m, 4H) , 7.70 (m, 4H) , 4.46 (t, 4H) , 2.05(m, 4H) , 1.47 (m, 4H) , 1.01 (m, 6H) ppm.

[0052] (3) 9,10-Diimidazole anthrathione ligand {[LR] ; Composition of (n=3)}

[0053]

[0054] The 9,10-diimidazole anthracene hexafluorophosphate salt {[AR](PF6)} obtained in step (2) 2; (n=3) (200 mg, 0.34 mmol) was added to a 100 mL round-bottom flask, dissolved in 60 mL of CH3CN, followed by the addition of sulfur powder (44 mg, 1.36 mmol) and potassium carbonate (188 mg, 1.36 mmol). The flask was then heated under stirring and reflux at 80 °C in an oil bath for 48 h in the dark. After the reaction was complete, the mixture was allowed to cool to room temperature, filtered, and the filter cake was extracted with dichloromethane. After removing the solvent by vortexing, 90 mg of the pale yellow product was collected, yielding 54%. The single crystal structure is shown in [reference needed]. Figure 1 . 1H NMR (400 MHz, CDCl3): δ = 7.54(s, 8H, He+f), 7.10 (d, 2H, Hb), 7.02 (d, 2H, Ha), 4.28(t, 4H, Hh), 1.99 (m,4H, Hi), 1.56 (m, 4H, Hj), 1.08 (t, 6H, Hk) ppm. 13 C{ 1 H} NMR (100 MHz, CDCl3): δ = 164.70(Cg), 131.49(Cc), 129.00(Cf), 127.76(Ce), 123.46(Cd), 119.85(Cb),118.09(Ca), 48.10(Ch), 31.14(Ci) , 19.98(Cj), 13.86(Ck) ppm. HRMS (ESI,positive ions): Calculated for [L1 + Na] + : 509.1804, found: 509.1738.

[0055] (4) Sandwich-type trinuclear platinum cluster-based cubic cage complex {[C8(LR)} 12 X 16 n=3, X=BF4 - The composition of}:

[0056]

[0057] Weigh out [Tr2Pt3(CH3CN)3][BF4]2 (50 mg, 0.047 mmol) and dissolve it in 6 mL of acetonitrile. After complete dissolution, a brownish-yellow solution is obtained. Weigh out the 9,10-diimidazole anthraquinone ligand {[LR]} obtained in step (3). ; (n=3)} (34 mg, 0.071 mmol) was dissolved in 3 mL of dichloromethane, and a solution of trinuclear Pt cluster acetonitrile (6 mL) was added dropwise to the 9,10-diimidazole anthraquinone ligand {[LR]} ; In a 3 mL solution of dichloromethane (n=3), the color immediately changed from pale yellow to orange-red. After stirring at room temperature in the dark for 12 h, the mixture was centrifuged. The resulting orange-red supernatant was concentrated to about 1 mL by rotary evaporation. A large amount of diethyl ether was added, and a large amount of orange-red precipitate immediately formed. After filtration and drying of the precipitate, 60 mg of orange-red solid powder was obtained, with a yield of 71%. The single crystal structure diagram is shown below. Figure 2 . 1H NMR (400 MHz, CD3CN): δ = 8.20 (m, 24H), 7.75 (m, 24H), 7.60 (m,24H), 7.49(s, 48H), 7.40(m, 24H), 3.85 (s, 56H), 3.41 (m, 48H), 2.95 (s,56H), 1.38 (m, 24H), 1.03 (m, 24H), 0.77 (m, 24H), 0.55 (m, 24H), -0.88 (m,72H) ppm. 13 C{ 1 H} NMR (100 MHz, CD3CN ): δ = 154.76, 131.27, 130.70, 129.52,129.45, 129.01, 124.31, 124.08, 123.93, 123.28, 56.80, 55.77, 49.67, 30.74,20.15, 13.72 ppm. HRMS (ESI, positive ions): calculated for [C 448 H 472 N 48 S 24 Pt 24 (BF4)8] 8+ :1584.3459, found: 1584.3347; calculated for [C 448 H 472 N 48 S 24 Pt 24 (BF4)9] 7+ :1823.0818, found: 1822.9843; calculated for [C 448 H 472 N 48 S 24 Pt 24 (BF4) 10 ] 6+ :2141.3963, found: 2141.4919.

[0058] Example 2 Sandwich Trinuclear Cluster-Based Cubic Cage Complex 2a

[0059]

[0060] The method for synthesizing the sandwich trinuclear cluster-based cubic cage complex described in this embodiment specifically includes the following steps:

[0061] (1) Synthesis of 9,10-diimidazole anthracene: The synthesis process and parameters are the same as those described in Example 1.

[0062] (2) Synthesis of 9,10-diimidazole anthracene hexafluorophosphate salt; the synthesis process is the same as that described in Example 1, except that bromobutane is replaced with methyl bromide, and the other parameters are the same.

[0063] (3) Synthesis of 9,10-diimidazole anthrone ligand; the synthesis process was the same as that described in Example 1, and the experimental conditions and raw material molar ratio were the same.

[0064] (4) Synthesis of sandwich-type trinuclear platinum cluster-based cubic cage complex; the synthesis process was the same as that described in Example 1, the experimental conditions and the molar ratio of the raw materials were the same, and the yield was 70%.

[0065] Example 3 Sandwich Trinuclear Cluster-Based Cubic Cage Complex 3a

[0066]

[0067] The method for synthesizing the sandwich trinuclear cluster-based cubic cage complex described in this embodiment specifically includes the following steps:

[0068] (1) Synthesis of 9,10-diimidazole anthracene: The synthesis process and parameters are the same as those described in Example 1.

[0069] (2) Synthesis of 9,10-diimidazole anthracene hexafluorophosphate salt; the synthesis process is the same as that described in Example 1, except that bromobutane is replaced with bromoethane, and the other parameters are the same.

[0070] (3) Synthesis of 9,10-diimidazole anthrone ligand; the synthesis process was the same as that described in Example 1, and the experimental conditions and raw material molar ratio were the same.

[0071] (4) Synthesis of sandwich-type trinuclear platinum cluster-based cubic cage complex; the synthesis process was the same as that described in Example 1, the experimental conditions and the molar ratio of the raw materials were the same, and the yield was 70%.

[0072] Example 4 Sandwich Trinuclear Cluster-Based Cubic Cage Complex 4a

[0073]

[0074] The method for synthesizing the sandwich trinuclear cluster-based cubic cage complex described in this embodiment specifically includes the following steps:

[0075] (1) Synthesis of 9,10-diimidazole anthracene: The synthesis process and parameters are the same as those described in Example 1.

[0076] (2) Synthesis of 9,10-diimidazole anthracene hexafluorophosphate salt; the synthesis process is the same as that described in Example 1, and the parameters are the same.

[0077] (3) Synthesis of 9,10-diimidazole anthrone ligand; the synthesis process was the same as that described in Example 1, and the experimental conditions and raw material molar ratio were the same.

[0078] (4) Synthesis of sandwich-type trinuclear platinum cluster-based cubic cage complex; The synthesis process is the same as that described in Example 1, and the raw material molar ratio is the same, except that [Tr2Pt3(CH3CN)3][BF4]2 is replaced with [Tr2Pt3(CH3CN)3][PF6]2, and the yield of the target product is 78%.

[0079] Example 5 Sandwich Trinuclear Cluster-Based Cubic Cage Complex 5a

[0080]

[0081] The method for synthesizing the sandwich trinuclear cluster-based cubic cage complex described in this embodiment specifically includes the following steps:

[0082] (1) Synthesis of 9,10-diimidazole anthracene: The synthesis process and parameters are the same as those described in Example 1.

[0083] (2) Synthesis of 9,10-diimidazole anthracene hexafluorophosphate salt; the synthesis process is the same as that described in Example 1, and the parameters are the same.

[0084] (3) Synthesis of 9,10-diimidazole anthrone ligand; the synthesis process was the same as that described in Example 1, and the experimental conditions and raw material molar ratio were the same.

[0085] (4) Synthesis of sandwich-type trinuclear platinum cluster-based cubic cage complex; The synthesis process is the same as that described in Example 1, and the raw material molar ratio is the same, except that [Tr2Pt3(CH3CN)3][BF4]2 is replaced with [Tr2Pt3(CH3CN)3][NO3]2, and the yield of the target product is 73%.

[0086] Example 6 Sandwich Trinuclear Cluster-Based Cubic Cage Complex 6a

[0087]

[0088] The method for synthesizing the sandwich trinuclear cluster-based cubic cage complex described in this embodiment specifically includes the following steps:

[0089] (1) Synthesis of 9,10-diimidazole anthracene: The synthesis process and parameters are the same as those described in Example 1.

[0090] (2) Synthesis of 9,10-diimidazole anthracene hexafluorophosphate salt; the synthesis process is the same as that described in Example 1, except that bromobutane is replaced with bromohexane, and the other parameters are the same.

[0091] (3) Synthesis of 9,10-diimidazole anthrone ligand; the synthesis process was the same as that described in Example 1, and the experimental conditions and raw material molar ratio were the same.

[0092] (4) Synthesis of sandwich-type trinuclear platinum cluster-based cubic cage complex; the synthesis process was the same as that described in Example 1, the experimental conditions and the molar ratio of the raw materials were the same, and the yield was 75%.

[0093] Adsorption dye property test:

[0094] Methyl orange dye molecules were dissolved in distilled water, and a certain amount of the sandwich-type trinuclear platinum cluster-based cubic cage complex {[C8(LR)} obtained in Example 1 was weighed. 12 X 16 n=3, X=BF4 - The powder was added to the methyl orange dye wastewater, and the dye and complex were mixed evenly in a water bath constant temperature shaker. After shaking for a certain period of time, the mixture was centrifuged, and the ultraviolet absorption spectrum of the solution was tested. The ultraviolet spectroscopy test was performed on an Agilent Cary-100 spectrophotometer.

[0095] The testing steps are as follows:

[0096] 1. Construction of the methyl orange standard curve: The simulated methyl orange dye wastewater solution was serially diluted to prepare solutions with concentrations of 1.0 × 10⁻⁶. -5 2.0×10 -5 3.0×10 -5 4.0×10 -5 5.0×10 -5 6.0×10 -5 The absorbance of a mol / L methyl orange solution was measured at the maximum absorption wavelength of 463 nm, using distilled water as a reference. The results are shown in Table 1. A standard curve was plotted, yielding the equation: y = 24742.8571x + 0.004, with a correlation coefficient R0. 2 =0.99996, such as Figure 3 As shown. Throughout the adsorption experiment, the absorbance of the methyl orange solution after adsorption was measured, and then converted to the concentration of the methyl orange solution after adsorption according to the standard curve equation. The adsorption rate P (%) and adsorption capacity Qe (mg·L⁻¹) were then calculated. -1 Adsorption rate P (%), adsorption capacity Qe (mg·L) -1 Calculate using the following formula:

[0097] ;

[0098] Table 1. Absorbance of methyl orange solutions at different concentrations

[0099] Absorbance A 0.25 0.50 0.75 0.99 1.24 1.49

[0100] 2. Investigating the effect of the amount of the target product complex added in Example 1 on the adsorption rate of methyl orange: The effect of the amount of the target product complex added in Example 1 on the adsorption rate of methyl orange is shown in Table 2 and... Figure 4 , Figure 5 The graph shows the change in UV absorption of methyl orange with the amount of the target product complex added in Example 1. When all other conditions were constant (room temperature 25 °C, 5 mL 3.0 × 10⁻⁶), the UV absorption of methyl orange was measured. -4 (Methyl orange solution, mol / L, shaken in water bath for 2 h). Changing the mass of the complex, the adsorption rate increases significantly with the increase of the complex mass. However, after the amount added exceeds 10 mg, the adsorption rate tends to level off with the increase of the complex mass. In order to save materials and achieve a high adsorption rate, 10 mg of cubic cages is selected as the optimal amount of adsorbent, at which time the adsorption rate is 98%.

[0101] Table 2 Effect of Complex Dosage on Adsorption Rate

[0102] Absorbance A of the dye after adsorption 3.72 3.21 1.86 0.86 0.19 0.12 Adsorption rate / % 50 57 75 88 98 98

[0103] 3. Investigating the effect of adsorption time on the adsorption rate of methyl orange: The effect of water bath shaking time on the adsorption rate of methyl orange is shown in Table 3 and... Figure 6 , Figure 7 The graph shows the change in UV absorption of methyl orange over adsorption time. When other conditions are constant (room temperature 25℃, 5 mL 3.0 × 10⁻⁶), the absorption rate is 10%. -4 A mol / L methyl orange solution was added with 10 mg of cubic cages. The shaking time was varied. When the shaking time was less than 100 min, the adsorption rate increased significantly with the extension of the shaking time. The adsorption rate reached 93% after shaking for 100 min. After 100 min, the increase in adsorption rate was slow. Considering efficiency, 140 min was selected as the optimal adsorption time.

[0104] Table 3 Effect of adsorption time on adsorption rate

[0105] Absorbance A of the dye after adsorption 2.63 1.92 0.99 0.52 0.27 0.15 0.10 0.08 Adsorption rate / % 63 74 87 93 96 98 99 99

[0106] 4. Investigating the effect of initial concentration on adsorption capacity: The initial concentration of the methyl orange dye solution was changed to investigate the effect of initial concentration on adsorption capacity. The results are shown in Table 4. Figure 8 Based on the Langmuir and Freundlich adsorption isotherm equations, plots were made with 1 / Qe against 1 / ce and lgQe against lgce. The fitting results are as follows: Figure 9 and Figure 10 As shown, the calculated correlation coefficients are listed in Table 5. Based on the Langmuir and Freundlich adsorption isotherm equations, plots were made with 1 / Qe against 1 / Ce and lgQe against lgCe: (1) The linear correlations were all in good agreement. (2) In the Freundlich adsorption isotherm equation, the parameter n = 1.04, n>1, indicating that the adsorption is a favorable adsorption process. (3) From the parameters of the Langmuir adsorption isotherm equation, it can be determined that there is a maximum saturation adsorption capacity during the adsorption process, which is 1533 mg·g -1 .

[0107] Table 4. Isothermal adsorption results of methyl orange dye wastewater by cubic cages at 25℃

[0108] Absorbance A 0.28 0.40 0.53 0.65 0.78 0.93 <![CDATA[Adsorption capacity / mg·g -1 > 63.67 71.03 78.40 85.76 93.13 100.33

[0109] Table 5. Relevant parameters of the Langmuir and Freundlich adsorption models.

[0110] LangmuirFreundlich <![CDATA[y=1.98012x+6.52286×10 -4 y=0.95752x-0.22859]]> <![CDATA[R 2 =0.9994 Q m =1533 mg·g -1 b=0.00033 L·mg -1 R 2 =0.99653 K F =0.59 n=1.04]]>

[0111] In addition to the above-mentioned adsorption applications, the cubic cage complexes described in this invention may also be used in molecular recognition, catalysis, drug delivery and sensing, and are expected to be used as next-generation materials.

[0112] The above description, in conjunction with specific preferred embodiments, provides a further detailed explanation of the present invention. It should not be construed that the specific implementation of the present invention is limited to these descriptions. For those skilled in the art, various simple deductions or substitutions can be made without departing from the concept of the present invention, and all such modifications and substitutions should be considered within the scope of protection of the present invention.

Claims

1. A sandwich-type trinuclear cluster-based cubic cage complex based on anthracene rings, characterized in that, The chemical structural formula of the complex is shown below: ； Where X is BF4 - PF6 - Or NO3 - Any one of them; R is selected from straight-chain alkyl groups having 1-8 carbon atoms.

2. The method for synthesizing the anthracene-based sandwich trinuclear cluster-based cubic cage complex according to claim 1, characterized in that: Starting with 9,10-dibromoanthracene and imidazole, a bidentate imidazole compound was first synthesized. Then, a bidentate imidazole hexafluorophosphate ligand was synthesized from the bidentate imidazole compound. Next, a bidentate organothione ligand was synthesized from the bidentate imidazole hexafluorophosphate ligand. Finally, an anthracene-based sandwich trinuclear cluster-based cubic cage complex was synthesized from the bidentate organothione ligand and a trinuclear platinum cluster. The structural formula of didentate imidazole compounds is: ; The structural formula of the didentate imidazole hexafluorophosphate ligand is as follows: R is a straight-chain alkyl group with 1-8 carbon atoms; The structural formula of the bidentate organothion ligand is: R is a straight-chain alkyl group with 1-8 carbon atoms; The trinuclear platinum cluster is [Tr2Pt3(CH3CN)3][X]2, where X = BF4. - PF6 - NO3 - The structural formula of the trinuclear platinum cluster is ; The structural formula of the anthracene-based sandwich trinuclear cluster-based cubic cage complex is as follows: X is BF4 - PF6 - Or NO3 - Any one; R is selected from straight-chain alkyl groups having 1-8 carbon atoms.

3. The synthesis method according to claim 2, characterized in that, Includes the following steps: (1) Synthesis of bidentate imidazole compounds 9,10-dibromoanthracene, imidazole, K2CO3, and CuSO4·5H2O were added to a sealed container, and then heated to carry out a coupling reaction. After the reaction was completed, the product was washed, filtered, dried, and chromatographically purified to obtain a bidentate imidazole compound. ； (2) Synthesis of didentate imidazole hexafluorophosphate salt ligands The didentate imidazole compound obtained in step (1) was dissolved in DMF solution, and RBr was added and heated in the dark to react. After the reaction was completed, the mixture was concentrated by rotary evaporation, and then ethyl acetate was added to produce a precipitate. The precipitate was filtered and dissolved in methanol. Then, a methanol solution of ammonium hexafluorophosphate was added to produce a precipitate. The mixture was stirred overnight at room temperature in the dark. After the reaction was completed, the didentate imidazole hexafluorophosphate ligand was obtained by filtration. In RBr, R is a straight-chain alkyl group with 1-8 carbon atoms. ； (3) Synthesis of bidentate organothione ligands The bidentate imidazole hexafluorophosphate salt ligand obtained in step (2) was dissolved in CH3CN, and sulfur powder and potassium carbonate were added. The mixture was then heated and stirred under reflux in the dark. After the reaction was completed, the bidentate organothione ligand was obtained by filtration and purification. ； (4) Synthesis of sandwich trinuclear cluster-based cubic cage complexes Weigh out the trinuclear platinum cluster [Tr2Pt3(CH3CN)3][X]2 and dissolve it in acetonitrile; weigh out the bidentate organothione ligand obtained in step (3) and dissolve it in dichloromethane; add the acetonitrile solution of the trinuclear platinum cluster [Tr2Pt3(CH3CN)3][X]2 to the dichloromethane containing the bidentate organothione ligand, stir the reaction at room temperature in the dark, then centrifuge and concentrate the supernatant by rotary evaporation, then add diethyl ether to precipitate the precipitate, and filter to obtain the sandwich trinuclear cluster-based cubic cage complex; wherein X in [Tr2Pt3(CH3CN)3][X]2 is BF4. - PF6 - Or NO3 - Any one of them; 。 4. The synthesis method according to claim 3, characterized in that: In step (1), the heating temperature for the heating coupling reaction is 180℃~200℃, and the reaction time is 36h.

5. The synthesis method according to claim 3, characterized in that: In step (1), the molar ratio of 9,10-dibromoanthracene, imidazole, K2CO3, and CuSO4·5H2O is 1.49:59.52:17.85:0.

59.

6. The synthesis method according to claim 3, characterized in that: In step (2), the heating temperature for the reaction in the dark is 110 °C and the reaction time is 24 h.

7. The synthesis method according to claim 3, characterized in that: In step (2), the molar ratio of the didentate imidazole compound, RBr, and ammonium hexafluorophosphate is 0.64:5.12:5.

12.

8. The synthesis method according to claim 3, characterized in that: In step (3), the reaction time for heating, stirring and refluxing in the dark is 48h; in step (4), the reaction time for stirring and refluxing at room temperature in the dark is 12h.

9. The synthesis method according to claim 3, characterized in that: In step (3), the molar ratio of the didentate imidazole hexafluorophosphate ligand, sulfur powder, and potassium carbonate is 0.34:1.36:1.

36.

10. The synthesis method according to claim 3, characterized in that: In step (4), the molar ratio of the trinuclear platinum cluster [Tr2Pt3(CH3CN)3][X]2 and the bidentate organothione ligand is 0.047:0.071.

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