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CN-122011045-A - Metal cage, ligand, preparation method and application thereof

CN122011045ACN 122011045 ACN122011045 ACN 122011045ACN-122011045-A

Abstract

The invention provides a metal cage, a ligand, a preparation method and application thereof, and relates to the technical field of metal-organic materials. The metal cage provided by the invention has the characteristics of asymmetric structure, large cavity size, stable property, high-efficiency and accurate identification of the fat-soluble dye, effective encapsulation, separation and release from a main body, excellent regeneration performance and recycling stability, can realize selective capture and controllable transportation of the fat-soluble dye, and provides a novel and efficient molecular carrier for the fields of dye separation and purification, environmental pollutant removal and the like.

Inventors

  • TONG JIN
  • LI BINGYU

Assignees

  • 北京工业大学

Dates

Publication Date
20260512
Application Date
20260413

Claims (10)

  1. 1. A metal cage is characterized in that the chemical expression of the metal cage is L 4 (bpyPd) 10 (X) 12 ; Wherein, the structural formula of L is shown as the following formula (I): (I); bpy is 2-2' bipyridine; The structural formula of the metal cage is shown as the following formula (II): (II); Wherein, the X is a balancing anion.
  2. 2. The metal cage of claim 1, wherein X is hexafluorophosphate.
  3. 3. A method of making a metal cage comprising: Will be The metal cage is prepared by solution self-assembly reaction with a (2-2' bipyridine) palladium complex; the structural formula of the (2-2' bipyridine) palladium complex is shown as the following formula (III): (III); Wherein, the Y is a counter anion.
  4. 4. A method for producing a metal cage according to claim 3, wherein, The molar ratio of the catalyst to the (2-2' -bipyridine) palladium complex is 2 (4.8-5.5).
  5. 5. The method according to claim 3 or 4, wherein when the counter anion of the metal cage is hexafluorophosphate, Y is nitrate, and the solution is subjected to an anion exchange reaction after self-assembly reaction to obtain the metal cage with the counter anion of hexafluorophosphate.
  6. 6. The method for preparing a metal cage according to claim 5, wherein the solvent used in the solution self-assembly reaction is water, and the temperature of the solution self-assembly reaction is 45-65 ℃.
  7. 7. A ligand, characterized in that the structural formula of the ligand is shown as the following formula (I): (I)。
  8. 8. A method for preparing a ligand, comprising the steps of: S1, carrying out a Suzuki-Miyaura coupling reaction on 2,4, 6-tribromopyridine and 1- (tetrahydro-2H-pyran-2-yl) -4- (4, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) -1H-pyrazole to prepare a compound A; s2, carrying out a Suzuki-Miyaura coupling reaction on the compound A and 4-pyridine boronic acid pinacol ester, and then carrying out hydrolysis deprotection to obtain the ligand; The synthetic route of the ligand is as follows: 。
  9. 9. Use of a metal cage according to claim 1 or 2 or a metal cage prepared by a method according to any one of claims 3 to 6 for separating dye molecules.
  10. 10. The use according to claim 9, wherein the dye molecule is a BODIPY boron fluoride dipyrrole dye molecule.

Description

Metal cage, ligand, preparation method and application thereof Technical Field The invention relates to the technical field of metal-organic materials, in particular to a metal cage, a ligand, a preparation method and application thereof. Background Supermolecule coordination compounds have been attracting attention due to their special structure, unique properties and potential application value, and in particular, countless supermolecule chemists have been devoted to designing and synthesizing supermolecule coordination compounds with novel structures and unique functions since the eighties of the twentieth century. The design and synthesis of the supermolecule coordination compound with novel structure and unique function is one of important research directions in the field of supermolecule chemistry. Because of its strong lipid solubility, the lipid-soluble dye may cross the blood brain barrier and affect the nervous system, with serious consequences and even genetic risks if we eat these contaminated animals and plants in an unknown state. In the prior art, conventional adsorption materials such as activated carbon, diatomite, silica gel, resin and the like are mostly used for separation and removal of fat-soluble dyes. However, the traditional adsorption material has inherent defects of limited adsorption capacity, single adsorption site, poor selective recognition capability on the fat-soluble dye and the like in practical application, and is difficult to realize specific capture and efficient enrichment on the target fat-soluble dye in a complex system, and meanwhile, the traditional adsorption material has the problem of poor chemical stability, so that structural collapse, swelling or decomposition is easy to occur in a practical use environment, and the adsorption performance is fast attenuated. In addition, after the traditional adsorption material is adsorbed, the problems of difficult desorption, harsh regeneration conditions, extremely low cyclic utilization rate and the like generally exist, the practical requirements on efficient, stable, green and sustainable separation treatment of the fat-soluble dye cannot be met, and the large-scale application of the fat-soluble dye in the field of accurate removal of the fat-soluble dye in a complex system is severely limited. Therefore, developing a novel adsorption material with high adsorption capacity, high selectivity, high stability, easy regeneration and recycling, realizing specific identification, efficient capturing and complete separation of fat-soluble dye, has become a key technical problem to be solved in the fields of environmental management, food safety and separation materials. Disclosure of Invention The invention provides a metal cage, a ligand and a preparation method and application thereof, which are used for solving the defects of limited adsorption capacity, poor selectivity, poor stability and low cyclic utilization rate of the traditional adsorption material in the prior art, and providing the metal cage with asymmetric structure, large cavity and stable property, thereby realizing efficient and accurate identification and capture of dye molecules. In a first aspect of the invention, a metal cage is provided, wherein the metal cage has a chemical expression of L 4(bpyPd)10(X)12; Wherein, the structural formula of L is shown as the following formula (I): (I); bpy is 2-2' bipyridine; The structural formula of the metal cage is shown as the following formula (II): (II); Wherein, the X is a balancing anion. The metal cage provided by the invention is a palladium-containing metal cage based on a pyrazolopyridine ligand, wherein the atomic radius of transition metal palladium is moderate, and the metal cage has a planar square coordination mode, so that the metal cage has special stability and functional diversity, side reactions are avoided to a large extent, and in addition, palladium has lower toxicity and relatively lower price. The metal cage provided by the invention has large cavity size and good water solubility, and can be used for effectively wrapping the fat-soluble dye by high-efficiency and accurate identification and then separating and releasing the fat-soluble dye from the main body. Preferably, the X is hexafluorophosphate. In a second aspect of the present invention, a method for preparing a metal cage is provided, comprising: Will be The metal cage is prepared by solution self-assembly reaction with a (2-2' bipyridine) palladium complex; the structural formula of the (2-2' bipyridine) palladium complex is shown as the following formula (III): (III); Wherein, the Y is a counter anion. As a preferred alternative to this,The molar ratio of the (2-2 '-bipyridine) palladium complex to the (2-2' -bipyridine) palladium complex is 2 (4.8-5.5), and can be, for example, 2:4.8, 2:4.9, 2:5.0, 2:5.1, 2:5.2, 2:5.3, 2:5.4 and 2:5.5, but is not limited to the recited values, other non-recited values in the numerical range are