Zirconium-based metal organic cage and preparation method thereof

Abstract

The invention relates to a zirconium-based metal organic cage and a preparation method thereof. The zirconium-based metal organic cage is synthesized by using an acceptor unit with electron-withdrawing capability as an organic ligand and coordinating with a zirconium-based metal source, and the acceptor unit with the electron-withdrawing capability is one or more of triazole, thiadiazole, selenadiazole, naphthalene thiadiazole and naphthalene selenadiazole. According to the present invention, the Zr-MOCs has good luminescence property, the luminescence covers the whole visible light range, the Zr-MOCs can be used for detection of different substances according to different emission behaviors, and the system regulation of the Zr-MOCs in the visible light range, the application of the Zr-MOCs in the luminescence field and the bioimaging aspect, the enrichment of the types of the luminescence MOCs, and the application of the Zr-MOCs in the bioimaging field are provided; the method has very important significance in promoting the application of the method in the fields of biological imaging and early diagnosis of diseases.

Description

Technical Field

[0001] The invention relates to the technical field of porous materials, in particular to a type of zirconium-based metal organic cage. Background Art

[0002] Porous luminescent materials have made important progress in the application fields of optics, sensing, fine molecular separation, catalysis, energy storage and conversion due to their open pore structure and adjustable pore environment. Among these porous materials, in addition to classic porous materials such as zeolites and activated carbons, metal-organic frameworks (MOFs), covalent organic frameworks (COFs) and discrete materials such as metal-organic cages (MOCs) and porous organic cages (POCs) have played an important role in various applications due to their adjustable structure and composition. Among them, the molecular nature of metal-organic cages (MOCs) gives them solution processability and structural diversity, so MOCs have received widespread attention.

[0003] MOCs are organic ligands coordinated with metal cations or metal oxide clusters to form structures with inherent pores. Currently, there is a lack of systematic research on luminescent Zr-MOCs. Summary of the invention

[0004] The technical problem to be solved by the present invention is to provide a type of zirconium-based metal organic cage.

[0005] In order to solve the above technical problems, the present invention adopts the following technical solutions: The invention relates to a zirconium-based metal organic cage, which is synthesized by using an acceptor unit with electron-withdrawing ability as an organic ligand coordinated with a zirconium-based metal source; the acceptor unit with electron-withdrawing ability is one or more of triazole, thiadiazole, selenadiazole, naphthiadiazole and naphthoselenadiazole.

[0006] Furthermore, the zirconium-based metal organic cage is a crystal, and the crystal structure is composed of six organic ligands and four (Cp)3Zr3(μ3-O)(μ2-OH)3 clusters; the crystal is a cubic crystal system with a Fm-3m space group.

[0007] In some embodiments, the luminescence properties of the synthesized zirconium-based metal organic cages are tuned by using organic ligands of acceptor units with different electron-withdrawing abilities, and are accordingly used for material detection or bioimaging.

[0008] In some embodiments, full-spectrum emitting metal-organic cages are synthesized using organic ligands of acceptor units with different electron-withdrawing abilities.

[0009] In some preferred embodiments, the zirconium-based metal source is bis(cyclopentadienyl)zirconium dichloride.

[0010] In some preferred embodiments, the organic ligand is one or more of the following compounds: .

[0011] In some preferred embodiments, zirconium-based metal-organic cage 1 is synthesized by H2BAMB, and its molecular formula is [Cp3Zr3O(OH)3]4(BAMB)6Cl4; zirconium-based metal-organic cage 2 is synthesized by H2BTMB, and its molecular formula is [Cp3Zr3O(OH)3]4(BTMB)6Cl4; zirconium-based metal-organic cage 3 is synthesized by H2BSMB, and its molecular formula is [Cp3Zr3O(OH)3]4(BSMB)6Cl4; zirconium-based metal-organic cage 4 is synthesized by H2NTMB, and its molecular formula is [Cp3Zr3O(OH)3]4(NTMB)6Cl4; zirconium-based metal-organic cage 5 is synthesized by H2NSMB, and its molecular formula is [Cp3Zr3O(OH)3]4(NSMB)6Cl4; the synthesis reaction is as follows: .

[0012] In some preferred embodiments, under the excitation of 365nm light, the maximum emission peaks of the zirconium-based metal-organic cages 1 to 5 are respectively at 439 nm for blue light range, 509 nm for cyan light range, 543 nm for green light range, 579 nm for yellow light range and 637nm for red light range, achieving full spectrum emission from blue light to red light; the ultraviolet-visible light absorption of the zirconium-based metal-organic cages 1 to 5 has maximum absorption values ​​of 400 nm, 475 nm, 500nm, 525nm and 600nm respectively.

[0013] The present invention provides a method for preparing a zirconium-based metal organic cage, comprising the following steps: The organic ligand and the zirconium-based metal source are added to a mixed solvent of appropriate amounts of diethylacetamide, tetrahydrofuran and water, mixed evenly, reacted at 40-60° C. for a predetermined time, and cooled to obtain the zirconium-based metal organic cage as described in any of the above embodiments.

[0014] In some embodiments, the relative amount of the organic ligand is 0.01-0.02 mmol; the relative amount of the zirconium-based metal source is 0.02-0.04 mmol; the relative amount of diethylacetamide is 0.5-2 mL, the relative amount of tetrahydrofuran is 0.5-2 mL, and the relative amount of water is 0.1-0.5 mL.

[0015] The beneficial effects of the present invention are: The zirconium metal organic cages (Zr-MOCs) in the present invention have good luminescence properties, and the luminescence covers the entire visible light range. It can be used to detect different substances according to different emission behaviors. The present invention is of great significance for the systematic regulation of Zr-MOCs in the visible light range, the application of Zr-MOCs in the field of luminescence and bio-imaging, enriching the types of luminescent MOCs, and promoting its application in bio-imaging and early disease diagnosis. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 It is a crystal photograph of the zirconium-based metal organic cage 1 according to an embodiment of the present invention.

[0017] Figure 2 It is a crystal photograph of the zirconium-based metal organic cage 3 according to an embodiment of the present invention.

[0018] Figure 3 It is a crystal photograph of the zirconium-based metal organic cage 4 according to an embodiment of the present invention.

[0019] Figure 4 It is a crystal photograph of the zirconium-based metal organic cage 5 according to an embodiment of the present invention.

[0020] Figure 5 1 is a fluorescence spectrum diagram of the zirconium-based metal organic cages 1 to 5 according to the embodiments of the present invention.

[0021] Figure 6 1 is the ultraviolet-visible light absorption spectrum of the zirconium-based metal organic cages 1 to 5 according to the embodiments of the present invention.

[0022] Figure 7 3 is a transient fluorescence lifetime decay diagram of the zirconium-based metal organic cages 1 to 5 according to the embodiments of the present invention.

[0023] Figure 8 1 is a crystal structure diagram of the zirconium-based metal organic cage 1 according to an embodiment of the present invention.

[0024] Fig. 9 1 is a crystal structure diagram of the zirconium-based metal organic cage 2 according to an embodiment of the present invention.

[0025] Fig.10 3 is a crystal structure diagram of the zirconium-based metal organic cage 3 according to an embodiment of the present invention. DETAILED DESCRIPTION

[0026] The exemplary embodiments of the present application will be described in more detail below with reference to the accompanying drawings. Although the exemplary embodiments of the present application are shown in the accompanying drawings, it should be understood that the present application can be implemented in various forms and should not be limited by the embodiments described herein. On the contrary, these embodiments are provided in order to enable a more thorough understanding of the present application and to fully convey the scope of the present application to those skilled in the art.

[0027] It should be understood that the terms used herein are only for the purpose of describing specific example embodiments and are not intended to be limiting. Unless the context clearly indicates otherwise, the singular forms "one", "an" and "said" as used herein may also be meant to include plural forms. The terms "include", "comprise", "contain", and "have" are inclusive, and therefore specify the existence of stated features, steps, operations, elements and / or parts, but do not exclude the existence or addition of one or more other features, steps, operations, elements, parts, and / or combinations thereof. The method steps, processes, and operations described herein are not interpreted as necessarily requiring them to be performed in the specific order described or illustrated, unless the execution order is clearly indicated. It should also be understood that additional or alternative steps may be used.

[0028] The experimental methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials described are commercially available unless otherwise specified.

[0029] The endpoints and any values ​​of the endpoint values ​​disclosed in the present invention are not limited to the precise range or value, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0030] The present invention is based on the perspective of molecular design and regulation, and the organic ligands used are: H2BAMB (4,4′-(2H-benzo[d][1,2,3]triazole-4,7-diyl)bis(3-methoxybenzoic acid)); H2BTMB (4,4'-(Benzo[c][1,2,5]thiadiazole-4,7-diyl)bis(3-methoxybenzoic acid)); H2BSMB (4,4'-(Benzo[c][1,2,5]selenadiazole-4,7-diyl)bis(3-methoxybenzoic acid)); H2NTMB (4,4'-(naphthol[2,3-c][1,2,5]thiadiazole-4,9-diyl)bis(3-methoxybenzoic acid)); H2NSMB (4,4'-(naphthol[2,3-c][1,2,5]selenothiazol-4,9-diyl)bis(3-methoxybenzoic acid)). The molecular structure of the organic ligand is: .

[0031] Here, introducing acceptor units with different electron-withdrawing abilities (triazole, thiadiazole, selenadiazole, naphthiadiazole, naphthoselenadiazole) to construct luminescent organic ligands with a donor-acceptor-donor (DAD) structure is an effective way to prepare zirconium-based metal organic cages with full-spectrum emission. The above organic ligands are coordinated with the Zr source provided by bis(cyclopentadienyl)zirconium dichloride to synthesize zirconium-based metal organic cages 1, 2, 3, 4 and 5 accordingly. The synthesis reaction formulas of zirconium-based metal organic cages 1 to 5 are as follows:

[0032] The single crystal diffraction of zirconium-based metal organic cages 1-5 was used to verify the product. The results showed that the crystal structure was composed of six organic ligands and four (Cp)3Zr3(μ3-O)(μ2-OH)3 clusters. By testing the optical properties of these five zirconium-based metal organic cages 1-5, the same donor unit and acceptor units with different electron-withdrawing abilities were used to successfully prepare metal organic cages with full spectrum emission, namely zirconium-based metal organic cages 1-5. According to the different luminescence properties of zirconium-based metal organic cages, they can be used in fields such as material detection or bioimaging. Example

[0033] In this embodiment, a zirconium-based metal organic cage 1 is synthesized, and its molecular formula is [Cp3Zr3O(OH)3]4(BAMB)6Cl4. The exemplary synthesis steps are as follows: Step 1: prepare a reaction system, wherein the reaction system comprises: The metal source is bis(cyclopentadienyl)zirconium dichloride, and the relative amount is 5.85 ~ 11.7 mg or 0.02 ~ 0.04 mmol; The organic ligand is H2BAMB, 4,4'-(2H-benzo[d][1,2,3]triazole-4,7-diyl)bis(3-methoxybenzoic acid), with a relative amount of 4.19 ~ 8.38 mg or 0.01 ~ 0.02 mmol; Solvent, relative amount of 1 mL diethylacetamide, relative amount of 1 mL tetrahydrofuran and relative amount of 0.2 mL water; Add the above reactants and solvent into a 5 mL vial and mix thoroughly by ultrasonication for 3-5 minutes; Step 2, the organic ligand and the metal source are coordinated and reacted, and the reaction is heated for a predetermined time. The heating temperature can be 40-60° C., for example, the reaction is placed in a 50° C. oven for 24 hours; Step 3: After cooling to room temperature, colorless cubic crystals of the zirconium-based metal organic cage 1 are obtained.

[0034] In the above steps, diethylacetamide, tetrahydrofuran and water are used as solvents to provide a reaction environment for the reactants. The amount of the above reactants can be appropriately adjusted based on the premise of sufficient reaction, the amount of each auxiliary agent can be appropriately adjusted based on the principle of complete reaction, and the amount of each component can be scaled according to the synthesis scale.

[0035] The crystal shape of the product was photographed using an optical microscope. Figure 1 The figure shows a crystal of zirconium-based metal organic cage 1. Single crystal diffraction was performed on cage 1 to verify the product and determine the crystal composition and structure. The single crystal diffraction results showed that cage 1 is a cubic crystal with a Fm-3m space group. The molecular formula of cage 1 is [Cp3Zr3O(OH)3]4(BAMB)6Cl4. Each cage 1 contains six H2BAMB (4,4'-(2H-benzo[d][1,2,3]triazole-4,7-diyl)bis(3-methoxybenzoic acid)) organic ligands and four (Cp)3Zr3(μ3-O)(μ2-OH)3 clusters, as shown in Figure 1. Figure 8 As shown; cage 1 has good optical properties, refer to Figure 5-6 The results of fluorescence and UV tests show that the maximum peak is 439nm and the maximum absorption range is 400nm, which can be used in the field of material detection. Example

[0036] This embodiment synthesizes zirconium-based metal organic cage 2[Cp3Zr3O(OH)3]4(BTMB)6Cl4, and the exemplary synthesis steps are: Step 1: prepare a reaction system, wherein the reaction system comprises: The metal source is bis(cyclopentadienyl)zirconium dichloride, and the relative amount is 5.85 ~ 11.7 mg or 0.02 ~ 0.04 mmol; The organic ligand is H2BTMB, 4,4'-(benzo[c][1,2,5]thiadiazole-4,7-diyl)bis(3-methoxybenzoic acid), with a relative amount of 4.36 to 8.72 mg or 0.01 to 0.02 mmol; Solvent, relative amount of 1 mL diethylacetamide, relative amount of 1 mL tetrahydrofuran and relative amount of 0.1 mL water; Add the above reactants and solvent into a 5 mL vial and mix thoroughly by ultrasonication for 3-5 minutes; Step 2, the organic ligand and the metal source are coordinated and reacted, and the reaction is heated for a predetermined time. The heating temperature can be 40-60° C., for example, the reaction is placed in a 50° C. oven for 24 hours; Step 3: After cooling to room temperature, pale yellow cubic crystals of zirconium-based metal organic cage 2 are obtained.

[0037] In the above steps, diethylacetamide, tetrahydrofuran and water are used as solvents to provide a reaction environment for the reactants. The amount of the reactants can be appropriately adjusted based on the premise of sufficient reaction, the amount of each auxiliary agent can be appropriately adjusted based on the principle of complete reaction, and the amount of each component can be scaled according to the synthesis scale.

[0038] Single crystal diffraction was performed on the product zirconium-based metal organic cage 2 to verify the product and determine the crystal composition and structure. The single crystal diffraction results showed that cage 2 was a cubic crystal with a Fm-3m space group. The molecular formula of cage 2 was [Cp3Zr3O(OH)3]4(BTMB)6Cl4. Each cage 2 was composed of six H2BTMB (4,4'-(benzo[c][1,2,5]thiadiazole-4,7-diyl)bis(3-methoxybenzoic acid)) organic ligands and four (Cp)3Zr3(μ3-O)(μ2-OH)3 clusters, such as Fig. 9 Cage 2 has good optical properties, see Figure 5-6 The results of fluorescence and UV tests showed that the maximum peak was 509nm and the maximum absorption range was 479nm, which can be used in the detection field. Example

[0039] This embodiment synthesizes zirconium-based metal organic cage 3[Cp3Zr3O(OH)3]4(BSMB)6Cl4, and the exemplary synthesis steps are as follows: Step 1: prepare a reaction system, wherein the reaction system comprises: The metal source is bis(cyclopentadienyl)zirconium dichloride, and the relative amount is 5.85 ~ 11.7 mg or 0.02 ~ 0.04 mmol; The organic ligand is H2BSMB, 4,4'-(benzo[c][1,2,5]selenadiazole-4,7-diyl)bis(3-methoxybenzoic acid), with a relative amount of 4.84 to 9.68 mg or 0.01 to 0.02 mmol; Solvent, relative amount of 1 mL diethylacetamide, relative amount of 1 mL tetrahydrofuran and relative amount of 0.2 mL water; Add the above reactants and solvent into a 5 mL vial and mix thoroughly by ultrasonication for 3-5 minutes; Step 2, the organic ligand and the metal source are coordinated and reacted, and the reaction is heated for a predetermined time. The heating temperature can be 40-60° C., for example, the reaction is placed in a 50° C. oven for 24 hours; Step 3: After cooling to room temperature, pale yellow cubic crystals of zirconium-based metal organic cage 3 are obtained.

[0040] In the above steps, diethylacetamide, tetrahydrofuran and water are used as solvents to provide a reaction environment for the reactants. The amount of the reactants can be appropriately adjusted based on the premise of sufficient reaction, the amount of each auxiliary agent can be appropriately adjusted based on the principle of complete reaction, and the amount of each component can be scaled according to the synthesis scale.

[0041] The crystal shape of the product zirconium-based metal organic cage 3 was photographed with an optical microscope, such as Figure 2 As shown, it is a zirconium-based metal organic cage 3 crystal. Single crystal diffraction was performed on cage 3 to verify the product and determine the crystal composition and structure. The single crystal diffraction results showed that cage 3 is a cubic crystal with Fm-3m space group. The molecular formula of cage 3 is [Cp3Zr3O(OH)3]4 (BSMB)6Cl4. Each cage 3 is composed of six H2BSMB (4,4'-(benzo[c][1,2,5]selenadiazole-4,7-diyl)bis(3-methoxybenzoic acid)) organic ligands and four (Cp)3Zr3(μ3-O)(μ2-OH)3 clusters, as shown in Figure 1. Fig.10 As shown. Cage 3 has good optical properties, refer to Figure 5-6 The results of fluorescence and UV tests show that the maximum peak is 543nm and the maximum absorption range is 500nm, which can be used in detection and other fields. Example

[0042] This embodiment synthesizes zirconium-based metal organic cage 4[Cp3Zr3O (OH)3]4(NTMB)6Cl4, and the exemplary synthesis steps are as follows: Step 1: prepare a reaction system, wherein the reaction system comprises: The metal source is bis(cyclopentadienyl)zirconium dichloride, and the relative amount is 5.85 ~ 11.7 mg or 0.02 ~ 0.04 mmol; The organic ligand is H2NTMB, 4,4'-(naphthol[2,3-c][1,2,5]thiadiazole-4,9-diyl)bis(3-methoxybenzoic acid), with a relative amount of 4.86 to 9.72 mg or 0.01 to 0.02 mmol; Solvent, relative amount of 1 mL diethylacetamide, relative amount of 1 mL tetrahydrofuran and relative amount of 0.2 mL water; Add the above reactants and solvent into a 5 mL vial and mix thoroughly by ultrasonication for 3-5 minutes; Step 2, the organic ligand and the metal source are coordinated and reacted, and the reaction is heated for a predetermined time. The heating temperature can be 40-60° C., for example, the reaction is placed in a 50° C. oven for 24 hours; Step 3: After cooling to room temperature, orange cubic crystals of zirconium-based metal organic cage 4 are obtained.

[0043] In the above steps, diethylacetamide, tetrahydrofuran and water are used as solvents to provide a reaction environment for the reactants. The amount of the reactants can be appropriately adjusted based on the premise of sufficient reaction, the amount of each auxiliary agent can be appropriately adjusted based on the principle of complete reaction, and the amount of each component can be scaled according to the synthesis scale.

[0044] The crystal shape was photographed using an optical microscope. Figure 3 The figure shows a zirconium-based metal organic cage 4 crystal. Single crystal diffraction was performed on cage 4 to verify the product and determine the crystal composition and structure. The single crystal diffraction results show that cage 4 is a cubic crystal with a Fm-3m space group. The molecular formula of cage 4 is [Cp3Zr3O (OH)3]4(NTMB)6Cl4. Each cage 4 is composed of six H2NTMB (4,4'-(naphthol [2,3-c][1,2,5]thiadiazole-4,9-diyl) bis (3-methoxybenzoic acid)) organic ligands and four (Cp)3Zr3(μ3-O)(μ2-OH)3 clusters. Cage 4 has good optical properties. Figure 5-6 The results of fluorescence and UV tests show that the maximum peak is 579nm and the maximum absorption range is 525nm, which can be used in detection and other fields. Example

[0045] In this embodiment, the zirconium-based metal organic cage 5[Cp3Zr3O(OH)3]4(NSMB)6Cl4 is synthesized, and the exemplary synthesis steps are as follows: Step 1: prepare a reaction system, wherein the reaction system comprises: The metal source is bis(cyclopentadienyl)zirconium dichloride, and the relative amount is 5.85 ~ 11.7 mg or 0.02 ~ 0.04 mmol; The organic ligand is H2NSMB, 4,4'-(naphthol[2,3-c][1,2,5]selenothiadiazole-4,9-diyl)bis(3-methoxybenzoic acid), with a relative amount of 5.34 to 10.68 mg or 0.01 to 0.02 mmol; Solvent, relative amount of 1 mL diethylacetamide, relative amount of 1 mL tetrahydrofuran and relative amount of 0.2 mL water; Add the above reactants and solvent into a 5 mL vial and mix thoroughly by ultrasonication for 3-5 minutes; Step 2, the organic ligand and the metal source are coordinated and reacted, and the reaction is heated for a predetermined time. The heating temperature can be 40-60° C., for example, the reaction is placed in a 50° C. oven for 24 hours; Step 3: After cooling to room temperature, red cubic crystals of zirconium-based metal organic cage 5 are obtained.

[0046] In the above steps, diethylacetamide, tetrahydrofuran and water are used as solvents to provide a reaction environment for the reactants. The amount of the reactants can be appropriately adjusted based on the premise of sufficient reaction, the amount of each auxiliary agent can be appropriately adjusted based on the principle of complete reaction, and the amount of each component can be scaled according to the synthesis scale.

[0047] The crystal shape was photographed using an optical microscope. Figure 4 The figure shows a zirconium-based metal organic cage 5 crystal. The single crystal diffraction of cage 5 was used to verify the product and determine the crystal composition and structure. The single crystal diffraction results show that cage 5 is a cubic crystal with Fm-3m space group. The molecular formula of cage 5 is [Cp3Zr3O(OH)3]4 (NSMB)6Cl4. Each cage 5 is composed of six H2NSMB (4,4'-(naphthol [2,3-c] [1,2,5] selenothiadiazole-4,9-diyl) bis (3-methoxybenzoic acid)) organic ligands and four (Cp)3Zr3(μ3-O)(μ2-OH)3 clusters. Cage 5 has good optical properties. Figure 5-6 The results of fluorescence and UV tests show that the maximum peak is 637nm and the maximum absorption range is 600nm, which can be used in detection and other fields.

[0048] Please refer to the fluorescence spectra of zirconium-based metal organic cages 1~5 Figure 5 ,Depend on Figure 5 It can be seen that under the excitation of 365nm light, the maximum emission peaks of zirconium-based metal organic cages 1, 2, 3, 4, and 5 are at 439 nm for blue light range, 509 nm for cyan light range, 543 nm for green light range, 579 nm for yellow light range, and 637 nm for red light range, respectively. From the fluorescence test results, it can be seen that the full spectrum emission from blue light to red light is achieved, indicating that the use of different electron-withdrawing groups can effectively regulate the luminescence properties of Zr-MOCs.

[0049] Please refer to the UV-Vis absorption spectra of zirconium-based metal organic cages 1~5 Figure 6 ,Depend on Figure 6 It can be seen that the maximum absorption values ​​of zirconium-based metal organic cages 1~5 are 400 nm, 475 nm, 500 nm, 525 nm, and 600 nm, indicating that the use of different electron-withdrawing groups can effectively regulate the light absorption properties of Zr-MOCs.

[0050] Please refer to the transient fluorescence lifetime decay diagram of zirconium-based metal organic cages 1~5 Figure 7 ,Depend on Figure 7 It can be seen that the lifetimes of cage 1, cage 2, cage 3, cage 4, and cage 5 are 1.36, 9.83, 7.48, 7.98, and 16.39 ns, respectively. From the test results, it is found that the greater the fluorescence emission and ultraviolet absorption, the longer the fluorescence lifetime.

[0051] The crystal structure diagram of zirconium-based metal organic cage 1-3 can be referred to Figure 8-10 ,Depend on Figure 8-10 It can be seen that the crystal structure of the base metal organic cage of the present invention is a tetrahedral type composed of 6 organic ligands and 4 (Cp)3Zr3(μ3-O)(μ2-OH)3 clusters.

[0052] The zirconium metal organic cages (Zr-MOCs) in the present invention have good luminescence properties, and the luminescence covers the entire visible light range, and can be used for the detection of different substances according to different emission behaviors. In addition, the present invention has very important significance for the systematic regulation of Zr-MOCs in the visible light range, the application of Zr-MOCs in the field of luminescence and bio-imaging, enriching the types of luminescent MOCs, and promoting their application in bio-imaging and early disease diagnosis.

[0053] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of protection of the present invention is defined by the appended claims and their equivalents.

Claims

1. The zirconium-based metal organic cage is synthesized by coordinating an electron-withdrawing acceptor unit as an organic ligand with a zirconium-based metal source; the electron-withdrawing acceptor unit is one or more of triazole, thiadiazole, selenadiazole, naphthiadiazole, and naphthoselenadiazole.

2. The zirconium-based metal organic cage according to claim 1, characterized in that: The zirconium-based metal organic cage is a crystal, and the crystal structure is composed of six organic ligands and four (Cp)3Zr3(μ3-O)(μ2-OH)3 clusters; the crystal is a cubic system with a Fm-3m space group.

3. The zirconium-based metal organic cage according to claim 1, characterized in that: The luminescence properties of the synthesized zirconium-based metal-organic cages are regulated by using organic ligands with different electron-withdrawing abilities of acceptor units, which are then used for material detection or bioimaging.

4. The zirconium-based metal organic cage according to claim 1, characterized in that: Metal-organic cages with full-spectrum emission were synthesized using organic ligands of acceptor units with different electron-withdrawing abilities.

5. The zirconium-based metal organic cage according to claim 1, characterized in that: The zirconium-based metal source is bis(cyclopentadienyl)zirconium dichloride.

6. The zirconium-based metal organic cage according to claim 5, characterized in that: The organic ligand is one or more of the following compounds: 。 7. The zirconium-based metal organic cage according to claim 6, characterized in that: The zirconium-based metal organic cage 1 was synthesized by H2BAMB, and the molecular formula was [Cp3Zr3O(OH)3]4 (BAMB)6Cl4; the zirconium-based metal organic cage 2 was synthesized by H2BTMB, and the molecular formula was [Cp3Zr3O(OH)3]4(BTMB)6Cl4; the zirconium-based metal organic cage 3 was synthesized by H2BSMB, and the molecular formula was [Cp3Zr3O(OH)3]4 (BSMB)6Cl4; the zirconium-based metal organic cage 4 was synthesized by H2NTMB, and the molecular formula was [Cp3Zr3O (OH)3]4(NTMB)6Cl4; the zirconium-based metal organic cage 5 was synthesized by H2NSMB, and the molecular formula was [Cp3Zr3O(OH)3]4 (NSMB)6Cl4; the reaction formula for synthesizing the zirconium-based metal organic cage is as follows: 。 8. The zirconium-based metal organic cage according to claim 7, characterized in that: Under the excitation of 365nm light, the maximum emission peak of zirconium-based metal organic cage 1 is at 439nm in the blue light range, the maximum emission peak of zirconium-based metal organic cage 2 is at 509nm in the cyan light range, the maximum emission peak of zirconium-based metal organic cage 3 is at 543nm in the green light range, the maximum emission peak of zirconium-based metal organic cage 4 is at 579nm in the yellow light range, and the maximum emission peak of zirconium-based metal organic cage 5 is at 637nm in the red light range, so as to obtain full spectrum emission from blue light to red light; The ultraviolet-visible light absorption of the zirconium-based metal-organic cage 1 has a maximum absorption value of 400 nm, the ultraviolet-visible light absorption of the zirconium-based metal-organic cage 2 has a maximum absorption value of 475 nm, the ultraviolet-visible light absorption of the zirconium-based metal-organic cage 3 has a maximum absorption value of 500 nm, the ultraviolet-visible light absorption of the zirconium-based metal-organic 4 has a maximum absorption value of 525 nm, and the ultraviolet-visible light absorption of the zirconium-based metal-organic cage 5 has a maximum absorption value of 600 nm.

9. A method for preparing a zirconium-based metal organic cage, comprising the following steps: The organic ligand and the zirconium-based metal source are added to a mixed solvent of appropriate amounts of diethylacetamide, tetrahydrofuran and water, mixed evenly, reacted at 40-60° C. for a predetermined time, and cooled to obtain the zirconium-based metal organic cage according to any one of claims 1 to 8.

10. The method according to claim 9, characterized in that: The relative amount of the organic ligand is 0.01~0.02 mmol; the relative amount of the zirconium-based metal source is 0.02~0.04 mmol; the relative amount of diethylacetamide is 0.5~2 mL, the relative amount of tetrahydrofuran is 0.5~2 mL, and the relative amount of water is 0.1~0.5 mL.

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