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A kind of thioether functionalized metal carboxylic acid molecular cage and its synthesis method

A metal carboxylic acid and functionalization technology, which is applied in chemical instruments and methods, copper organic compounds, and other chemical processes, can solve the problems of not being able to use metal ions, etc., and achieve unique aesthetic value, unique structure, and rich valence states Effect

Active Publication Date: 2017-04-19
GUANGDONG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] Although supramolecular cages based on aromatic carboxylic acid ligands have been reported, there are few reports on the assembly of thioether-functionalized supramolecular cages by introducing thioether side chains into ligands. is a big challenge
In addition, the functionality of metal carboxylic acid molecular cages in the prior art is limited to adsorbing and storing gases, and cannot be used to support metal ions
Therefore, the functionality of such metal carboxylic acid molecular cages remains to be further developed.

Method used

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  • A kind of thioether functionalized metal carboxylic acid molecular cage and its synthesis method
  • A kind of thioether functionalized metal carboxylic acid molecular cage and its synthesis method
  • A kind of thioether functionalized metal carboxylic acid molecular cage and its synthesis method

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Embodiment 1

[0045] A kind of thioether functionalized metal carboxylic acid molecular cage of the present embodiment has a chemical formula of C 408 h 384 o 120 S 72 Cu 24 , and the chemical structural formula shown in formula I:

[0046]

[0047] Formula I.

[0048] Among them, in the chemical structural formula represented by formula I, the copper atom adopts a hexacoordinated octahedral configuration, and every two copper atoms form a two-copper cluster, and the bond length of the Cu-Cu bond in the two-copper cluster is 2.734(1) Å, Each dicopper cluster is coordinated with ten O atoms, among which, eight of the ten O atoms come from the carboxylic acid functional groups on the four ligands, and the other two of the ten O atoms come from the Two coordinated water molecules, and the two coordinated water molecules are respectively located at the axial position of the Cu–Cu bond in the two copper clusters.

[0049] among them, see figure 1 , the thioether functionalized metal c...

Embodiment 2

[0053] A kind of synthetic method of thioether functionalized metal carboxylic acid molecular cage of the present embodiment, it comprises the following steps:

[0054] Step 1, the preparation of intermediate product 3',4',5'-tri(methylthio)biphenyl-3,5-dimethyl ester

[0055] Put 5-bromo-1,2,3-trithiomethylbenzene, 3,5-dimethoxycarbonylphenylboronic acid, potassium carbonate and catalyst tetraphenylphosphine palladium into two-necked round-bottomed flasks, and Add the deoxygenated organic solvent ethylene glycol dimethyl ether into the bottom flask, and then under the protection of nitrogen, pass nitrogen gas into the two-necked round bottom flask, and then react at 85°C for 60h to obtain the reaction solution. After cooling, pour the reaction solution into water (the water in this embodiment is distilled water), add dichloromethane for extraction, then use a rotary evaporator to remove the organic solvent, and the remaining substances after removing the organic solvent pass ...

Embodiment 3

[0064] A kind of synthetic method of thioether functionalized metal carboxylic acid molecular cage of the present embodiment, it comprises the following steps:

[0065] Step 1, the preparation of intermediate product 3',4',5'-tri(methylthio)biphenyl-3,5-dimethyl ester

[0066] Put 5-bromo-1,2,3-trithiomethylbenzene, 3,5-dimethoxycarbonylphenylboronic acid, sodium carbonate and catalyst tetraphenylphosphine palladium in two-necked round-bottomed flasks, and Add deoxygenated organic solvent toluene into the bottom flask, and then pass nitrogen gas into the two-necked round-bottomed flask under the protection of nitrogen, and then react at 90°C for 48 hours to obtain a reaction solution. After the reaction solution is cooled, the reaction Liquid is poured into water (the water in this embodiment is distilled water), and dichloromethane is added for extraction, and then the organic solvent is removed by a rotary evaporator, and the remaining substances are separated and purified by ...

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Abstract

The invention relates to the technical field of materials in the light industry and the chemical industry, in particular to a thioether-functionalized metal carboxylate molecular cage and a synthetic method thereof. The chemical formula of the thioether-functionalized metal carboxylate molecular cage is C408H384O120S72Cu24, and the thioether-functionalized metal carboxylate molecular cage adopts a cubic crystal structure. The synthetic method comprises the following steps: step 1, preparing an intermediate product 3',4',5'-tris(methylmercapto)biphenyl-3,5-dimethyl ester; step 2, preparing a thioether-functionalized ligand 3',4',5'- tris(methylmercapto)biphenyl-3,5-dicarboxylic acid; step 3, enabling reaction between the thioether-functionalized ligand and Cu(NO3)2.3H2O to finally synthesize the thioether-functionalized metal carboxylate molecular cage in the form of a blue polyhedral bulk crystal. The thioether-functionalized metal carboxylate molecular cage can be loaded with metal ions, can serve as a carrier of a palladium catalyst and can also be used for treating mercury-polluted water.

Description

technical field [0001] The invention relates to the technical field of light industry and chemical materials, in particular to a sulfide functionalized metal carboxylic acid molecular cage and a synthesis method thereof. Background technique [0002] In recent years, with the development of supramolecular chemistry, a metal-organic molecular cage material with high symmetry has attracted extensive attention. This material not only has an attractive and unique aesthetic structure, but also has broad application prospects in the fields of molecular recognition, host-guest chemistry, and catalysis. This molecular cage structure is mainly composed of 12 metal-metal clusters and 24 ligands, and each molecular cage has eight equilateral triangles and six square windows. The entire polyhedral molecular cage is a discrete molecular structure, and There is a large hole inside, which can be a guest molecule (such as CH 4 、H 2 , CO 2 etc.) offers the possibility of adsorption stora...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F1/08B01J20/22
CPCB01J20/226B01J2220/44C07F1/08
Inventor 何军曹鹏黄建何永和黄家鸿
Owner GUANGDONG UNIV OF TECH
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