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CN-122011038-A - Linear Pt (NHC) for constructing MOFs2Metal organic carboxylic acid ligand, preparation method and application thereof

CN122011038ACN 122011038 ACN122011038 ACN 122011038ACN-122011038-A

Abstract

The invention discloses a linear Pt (NHC) 2 metal-organic carboxylic acid ligand for constructing MOFs, a preparation method and application thereof, wherein the linear Pt (NHC) 2 metal-organic carboxylic acid ligand for constructing MOFs comprises H 2 PPyDC-Pt(NHC) 2 and H 2 DPPyDC-Pt(NHC) 2 , and particularly discloses a preparation method of the linear Pt (NHC) 2 metal-organic carboxylic acid ligand and application thereof in constructing metal-organic frame materials or metal-organic thin layer materials, and the constructed materials have better optical performance and catalytic performance.

Inventors

  • HU XUEFU
  • LIU QINGQING
  • ZHANG XIULI
  • CHEN LIYONG
  • LI YANG
  • WANG SHUO
  • JIANG HAO
  • SU CHANG

Assignees

  • 蚌埠医科大学

Dates

Publication Date
20260512
Application Date
20260115

Claims (9)

  1. 1. A linear Pt (NHC) 2 metal organic carboxylic acid ligand for constructing MOFs is characterized in that the linear Pt (NHC) 2 metal organic carboxylic acid ligand comprises H 2 PPyDC-Pt(NHC) 2 and H 2 DPPyDC-Pt(NHC) 2 , and the corresponding structural formulas are as follows: 、 。
  2. 2. A method for preparing the linear Pt (NHC) 2 metal-organic carboxylic acid ligand of claim 1, wherein the linear Pt (NHC) 2 metal-organic carboxylic acid ligand H 2 PPyDC-Pt(NHC) 2 is synthesized by the following steps: 。
  3. 3. The method for preparing a linear Pt (NHC) 2 metal-organic carboxylic acid ligand according to claim 2, characterized in that the specific synthesis steps of the linear Pt (NHC) 2 metal-organic carboxylic acid ligand H 2 PPyDC-Pt(NHC) 2 are: Step S1, dissolving 6-bromomethyl nicotinate and 4-methoxycarbonyl phenylboric acid in ethylene glycol dimethyl ether to prepare a mixed solution, adding tetraphenylphosphine palladium as a catalyst and a potassium carbonate aqueous solution, carrying out a reaction at 90-110 ℃ under the condition of nitrogen after deoxidization, directly evaporating to dryness after the reaction is finished, extracting with dichloromethane and water, evaporating an organic layer to dryness, and washing with ethanol to obtain a yellow solid product Me 2 PPyDC; step S2, dissolving Me 2 PPyDC and potassium tetrachloroplatinate in a mixed solution of 2-ethoxyethanol and water to prepare a mixed solution, carrying out a reaction at 70-90 ℃ under the condition of nitrogen after deoxidization, and directly filtering after the reaction is completed and cooling to obtain an orange solid product (Me 2 PPyDC-Pt) 2 ; S3, dissolving (Me 2 PPyDC-Pt) 2 and 3,3' -methylenebis (1-methyl-3-imidazolium bromide) in dimethyl sulfoxide to prepare a mixed solution, adding triethylamine, deoxidizing, reacting at 80-100 ℃ under the condition of nitrogen, cooling to room temperature after the reaction is finished, extracting with dichloromethane and saturated saline, evaporating an organic layer, and recrystallizing with ethanol to obtain a yellow solid product Me 2 PPyDC-Pt(NHC) 2 ; And S4, dissolving Me 2 PPyDC-Pt(NHC) 2 and sodium hydroxide in a mixed solution of water and ethanol to prepare a mixed solution, reacting at 80-100 ℃, completely cooling to room temperature, evaporating ethanol in the system, acidifying with hydrochloric acid at 0 ℃, and obtaining a yellow solid product H 2 PPyDC-Pt(NHC) 2 after centrifugal separation and water washing.
  4. 4. A method for preparing the linear Pt (NHC) 2 metal-organic carboxylic acid ligand of claim 1, wherein the linear Pt (NHC) 2 metal-organic carboxylic acid ligand H 2 DPPyDC-Pt(NHC) 2 is synthesized by the following steps: 。
  5. 5. The method for preparing a linear Pt (NHC) 2 metal-organic carboxylic acid ligand according to claim 4, wherein the specific synthesis steps of the linear Pt (NHC) 2 metal-organic carboxylic acid ligand H 2 DPPyDC-Pt(NHC) 2 are: S1, dissolving 2, 5-dibromopyridine and 4-methoxycarbonyl phenylboric acid in N, N-dimethylformamide to prepare a mixed solution, adding palladium acetate and tricyclohexylphosphine as catalysts, adding a potassium phosphate aqueous solution, carrying out reaction at 130-150 ℃ under the condition of nitrogen after deoxidization, filtering while the reaction is finished, directly evaporating to dryness, extracting with dichloromethane and water, evaporating an organic layer to dryness, and washing with ethanol to obtain a yellow solid product Me 2 DPPyDC; Step S2, dissolving Me 2 DPPyDC and potassium tetrachloroplatinate in a mixed solution of 2-ethoxyethanol and water to prepare a mixed solution, carrying out a reaction at 80-100 ℃ under the condition of nitrogen after deoxidization, and directly filtering after the reaction is completed and cooling to obtain a yellow solid product (Me 2 DPPyDC-Pt) 2 ; S3, dissolving (Me 2 DPPyDC-Pt) 2 and 3,3' -methylenebis (1-methyl-3-imidazolium bromide) in dimethyl sulfoxide to prepare a mixed solution, adding triethylamine, carrying out a reaction at 80-100 ℃ under the condition of nitrogen after deoxidization, carrying out extraction with dichloromethane and saturated saline after the reaction is completed and the reaction is cooled to room temperature, taking an organic layer, evaporating to dryness, and carrying out recrystallization with ethanol to obtain a brown yellow solid product Me 2 DPPyDC-Pt(NHC) 2 ; And S4, dissolving Me 2 DPPyDC-Pt(NHC) 2 and sodium hydroxide into a mixed solution of water and ethanol to prepare a mixed solution, reacting at 90-100 ℃, cooling to room temperature after the reaction is finished, evaporating ethanol in the system, acidifying with hydrochloric acid at 0 ℃, and obtaining a brown yellow solid product H 2 DPPyDC-Pt(NHC) 2 after centrifugal separation and water washing.
  6. 6. Use of the linear Pt (NHC) 2 metal-organic carboxylic acid ligand of claim 1 in the construction of metal-organic framework materials or metal-organic thin layer materials.
  7. 7. The method according to claim 6, wherein the metal organic framework material MOFs-Pt is constructed based on the linear Pt (NHC) 2 metal organic carboxylic acid ligand H 2 PPyDC-Pt(NHC) 2 , which is characterized in that ligand H 2 PPyDC-Pt(NHC) 2 , metal compound HfCl 4 /ZrCl 4 , solvent DMF and modifier acetic acid are added into a serum bottle, the mixture is uniformly mixed by ultrasound and then reacted at 80-100 ℃, the reaction is cooled to room temperature, the obtained solid is centrifugally separated and washed with fresh DMF for a plurality of times to obtain yellow solid, the yellow solid is dried to obtain MOFs material which is denoted MOFs-Pt, and the corresponding synthetic route is as follows: 。
  8. 8. The method of preparing MOFs-Pt-E based on the metal organic carboxylic acid ligand H 2 PPyDC-Pt(NHC) 2 of linear Pt (NHC) 2 is characterized by comprising the specific steps of adding ligand H 2 PPyDC, metal compound HfCl 4 /ZrCl 4 , solvent DMF and modifier acetic acid into a serum bottle, carrying out ultrasonic mixing uniformly, reacting at 100-120 ℃, cooling to room temperature after the reaction is finished, centrifuging to obtain MOFs solid, preparing an H 2 PPyDC-Pt(NHC) 2 solution from ligand H 2 PPyDC-Pt(NHC) 2 , dispersing the prepared MOFs solid into the H 2 PPyDC-Pt(NHC) 2 solution to form a dispersion liquid, stirring the dispersion liquid at 100-120 ℃, carrying out centrifugal separation to obtain yellow solid after the reaction, washing the yellow solid with fresh DMF for a plurality of times, and drying to obtain MOFs material, namely MOFs-Pt-E, wherein the corresponding synthetic route is as follows: 。
  9. 9. The method according to claim 6, wherein the construction of MOFs-Pt-D based on linear Pt (NHC) 2 metal-organic carboxylic acid ligand H 2 PPyDC-Pt(NHC) 2 comprises the steps of adding ligand H 2 PPyDC, ligand H 2 PPyDC-Pt(NHC) 2 , metal compound HfCl 4 /ZrCl 4 , solvent DMF and modifier acetic acid into a serum bottle, carrying out ultrasonic mixing uniformly, reacting at 80-100 ℃, cooling to room temperature after the reaction is completed, obtaining a solid through centrifugal separation, washing the solid with fresh DMF for a plurality of times to obtain yellow solid, and drying to obtain MOFs material, namely MOFs-Pt-D, wherein the corresponding synthetic route is as follows: 。

Description

Linear Pt (NHC) 2 metal organic carboxylic acid ligand for constructing MOFs, preparation method and application thereof Technical Field The invention belongs to the technical field of preparation of organic ligands for MOFs construction, and particularly relates to a linear Pt (NHC) 2 metal organic carboxylic acid ligand for constructing MOFs, and a preparation method and application thereof. Background Platinum (II) carbene (Pt-carbene) metal-organic complexes, in particular complexes based on N-heterocyclic carbenes (NHC), are a research hotspot and leading-edge area for modern metal-organic chemistry and materials science. The combination of the strong sigma electron donating ability and excellent stability of NHC and the unique photophysical properties (such as phosphorescence and long-life excited state) of platinum metal can prepare the platinum metal organic complex with more excellent properties. The platinum (II) carbene metal organic complex has wide application, can be used as an excellent anticancer drug in the field of biological medicine, can be used as an excellent yellow fluorescent powder material in the field of luminescence, is used for an LED which is compounded with blue light to form white light, and can be used as a catalyst to show excellent catalytic performance in the catalytic process of various chemical reactions. Meanwhile, the platinum (II) has a d 8 closed shell electron structure, when two molecules of platinum (II) complex are separated from each other, a metal-philic interaction (Metallophilicity) and MMLCT (metal-ligand charge transfer) process exists, so that the properties of the platinum complex, such as catalytic reaction promotion, reaction efficiency improvement, photon yield improvement and the like, can be further improved. The homogeneous catalysis system has high reaction efficiency and no diffusion limitation of substrate, but has many problems in the reaction process, such as poor catalyst stability and short service life, difficult separation and recovery from the reaction system, difficult recycling, high cost, difficult separation from the product, influence on purification of the product, and additional increase of the purification energy consumption of the product, and difficult regulation and control of the distance between the metal platinum and the platinum in the complex in the homogeneous system, and difficult generation of platinum-platinum interaction, thereby limiting the application of the platinum metal organic complex. MOFs material is an organic-inorganic hybrid crystalline material developed in the last thirty years, and has the characteristics of controllable structure synthesis, simple method, easy separation and recovery from a system, precise structure, definite atomic site, strong designability, adjustable pore canal size and the like. Therefore, MOFs materials become ideal catalytic and drug delivery support materials. The method comprises the steps of fixing a platinum (II) metal organic complex by using MOFs, providing a special microenvironment for the platinum (II) metal organic complex by using MOFs framework to improve stability of the platinum (II) metal organic complex, and realizing precise control of a platinum-platinum distance by using designability of MOFs structure through MOFs configuration adjustment so as to realize a metallophilic interaction and MMLCT process, improve performance of the Pt-metal organic complex, and realize regulation and control of optical and catalytic performances by using distance control between metal Pt, thereby providing platform support for research of a structure-activity relationship of the platinum-platinum organic complex. If the synthesis of the designed metal organic ligand based on Pt (NHC) 2 can be realized, the construction of MOFs with various configurations can be realized, thereby realizing the regulation and control of the performance of the Pt-metal organic complex. Disclosure of Invention The invention solves the technical problem of providing a linear Pt (NHC) 2 metal-organic carboxylic acid ligand for constructing MOFs, a preparation method and application thereof, wherein the method firstly prepares a required ligand, and then synthesizes a target product of double-carbene (NHC) coordinated linear metal-organic complex ligand based on Pt (NHC) 2 by a coordination chemistry and metal-organic chemistry method, and the ligand can be used for constructing MOFs materials and the constructed MOFs materials have good optical performance and catalytic performance. The invention adopts the following technical scheme to solve the technical problems, and is a linear Pt (NHC) 2 metal organic carboxylic acid ligand for constructing MOFs, wherein the linear Pt (NHC) 2 metal organic carboxylic acid ligand comprises H 2PPyDC-Pt(NHC)2 and H 2DPPyDC-Pt(NHC)2, and the corresponding structural formulas are respectively as follows: 、。 The invention relates to a preparation method of a linear Pt (