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CN-117402106-B - Multidentate organic ligand containing triphenylamine-terpyridine structure, metal supermolecular polymer, polymer film and preparation method

CN117402106BCN 117402106 BCN117402106 BCN 117402106BCN-117402106-B

Abstract

The invention provides a polydentate organic ligand containing triphenylamine-terpyridine structure, a metal supermolecular polymer, a polymer film and a preparation method thereof, belonging to the technical field of organic luminescent materials. The invention designs and synthesizes a novel multidentate organic ligand containing a triphenylamine-terpyridine structure, and by introducing an electron donating group at the para position of a benzene ring, the oxidation-reduction potential can be effectively reduced, the electrochromic efficiency is enhanced, the entry and extraction of ions and electrons are promoted, and the ligand is coordinated with metal ions to drive and synthesize a series of metal supermolecular polymers, so that the prepared metal-supermolecular polymer film has short color change response time and high electrochromic performance.

Inventors

  • ZHAO XIAOGANG
  • WU YUQI
  • CONG BING
  • WANG DAMING
  • ZHOU HONGWEI
  • CHEN CHUNHAI

Assignees

  • 吉林大学

Dates

Publication Date
20260512
Application Date
20231018

Claims (9)

  1. 1. A multidentate organic ligand containing a triphenylamine-terpyridine structure, which is characterized by having a structure shown in a formula I: I is a kind of Wherein R 1 is selected from one of the following structures: ; R 2 is selected from one of the following structures: 。
  2. 2. A method for preparing a multidentate organic ligand according to claim 1, comprising the steps of: (1) Under alkaline condition, 4-nitrobenzaldehyde and 2-acetyl pyridine are used as raw materials, and 4'- (4-nitrophenyl) -2,2':6', 2' -terpyridine is synthesized by a one-pot method; (2) Under inert atmosphere, 4'- (4-nitrophenyl) -2,2':6', 2' -terpyridine obtained in the step (1) is subjected to reduction reaction with hydrazine hydrate under the condition of catalyst Pd/C to obtain 4'- (4-aminophenyl) -2,2':6', 2' -terpyridine; (3) Under alkaline condition, 4'- (4-aminophenyl) -2,2':6', 2' -terpyridine and iodobenzene compound obtained in step (2) react with 18-crown ether-6 under the action of copper powder as catalyst to obtain terpyridine aniline compound; (4) Under alkaline condition, the terpyridyl aniline compound obtained in the step (3) and a dibromo compound react with 18-crown ether-6 under the action of copper powder as a catalyst to obtain a target product; The structural formula of the iodobenzene compound is ; The structural formula of the dibromo compound is ; Wherein R 2 in the iodobenzene compound is consistent with R 2 in claim 1, and R 1 in the dibromo compound is consistent with R 1 in claim 1.
  3. 3. The preparation method of the aqueous alkali composite material is characterized in that in the step (1), alkali is potassium hydroxide and ammonium hydroxide, the molar ratio of the 4-nitrobenzaldehyde to the 2-acetylpyridine to the potassium hydroxide to the ammonium hydroxide is 1 (1.5-4): 1-5, the reaction temperature of the one-pot method is room temperature, and the reaction time is 72-96 hours.
  4. 4. The preparation method of the hydrazine hydrate, which is characterized in that the mass fraction of the hydrazine hydrate in the step (2) is 65% -85%, the molar ratio of the 4'- (4-nitrophenyl) -2,2':6', 2' -terpyridine to the hydrazine hydrate is 1 (5% -15), the reduction reaction temperature is 70-80 ℃, and the reaction time is 8-15 h.
  5. 5. The preparation method of the Ullmann reaction catalyst is characterized in that the base in the step (3) is potassium carbonate, the mole ratio of 4'- (4-aminophenyl) -2,2':6', 2' -terpyridine: iodobenzene compound: copper: potassium carbonate: 18-crown ether-6 is 1 (1-3): 0.4-0.6, and the reaction temperature of the Ullmann reaction is 140-175 ℃, and the reaction time is 12-20 h.
  6. 6. The preparation method of the catalyst according to claim 2, wherein the alkali in the step (4) is potassium carbonate, the molar ratio of the terpyridyl aniline compound to the dibromo compound to the copper to the potassium carbonate to the 18-crown ether-6 is 1 (0.5-1.5): (1-3): (0.4-0.6), and the reaction temperature of the Ullmann reaction is 140-175 ℃ and the reaction time is 10-40 h.
  7. 7. A metal supramolecular polymer synthesized by coordination driving of a multidentate organic ligand according to claim 1 with a metal ion; The metal ion is selected from Fe(BF 4 ) 2 ·6H 2 O、Cu(ClO 4 ) 2 ·6H 2 O、Zn(BF 4 ) 2 ·6H 2 O、RuCl 2 (DMSO) 4 .
  8. 8. The metal supramolecular polymer of claim 7, wherein the molar ratio of multidentate organic ligand to metal ion is 1 (1-2).
  9. 9. A metal ion-ligand supramolecular polymer film, which is characterized in that the metal supramolecular polymer according to any one of claims 7-8 is dissolved in methanol, then sprayed on the surface of ITO conductive glass, and dried.

Description

Multidentate organic ligand containing triphenylamine-terpyridine structure, metal supermolecular polymer, polymer film and preparation method Technical Field The invention relates to the technical field of organic luminescent materials, in particular to a polydentate organic ligand containing triphenylamine-terpyridine structure, a metal supermolecular polymer, a polymer film and a preparation method. Background The metal supermolecular polymer is a novel electrochromic material, which is prepared by coordination polymerization of small organic molecules or polymers and metal ions, and shows electrochromic characteristics mainly based on metal-ligand charge transfer. The metal center of the polymer is combined with the main chain or the side chain of the polymer, so that the advantages of the organic material and the inorganic material can be supplemented and combined. The coordination polymer electrochromic film prepared based on molecular assembly not only has excellent coloring efficiency and oxidation-reduction stability, but also can adjust the color of the material by modifying an organic ligand or changing the metal ion type, thereby realizing wide color change. Triphenylamine is an excellent electroactive group. The triphenylamine electrochromic material has the greatest characteristics of a short conjugated structure and a high energy band gap, is colorless in a neutral state and has obvious color change in an oxidation process, and the characteristics well meet the energy-saving requirement of the electrochromic material. Meanwhile, the three-dimensional large-volume twisted structure of the triphenylamine weakens the solid pi-pi stacking effect of the material. In conclusion, the intermediate state colorless electrochromic material capable of being processed by solution can be prepared by introducing triphenylamine structure into the metal supermolecular polymer. Pyridine and its derivatives can be used as a luminescent material not only as a heterocyclic organic luminescent molecule per se, but also as a raw material for exploring and synthesizing a better luminescent material. 2,2':6', 2' -terpyridine (tpy) is a common tridentate ligand, and not only can coordinate with metal to form a < tpy-M 2+ -tpy > complex with a stable primitive, but also has a large pi conjugated structure, so that the complex itself has strong sigma electron donating ability and pi electron accepting ability. This imparts the abundant photophysical and electrochemical properties to the terpyridine metal complex. Most terpyridine metal complexes have the characteristics of adjustable emission wavelength, long emission service life, large Stokes displacement, good optical stability and the like, and are widely expanded to the fields of photoluminescence, catalysts, self-assembly, sensing, biological imaging and the like. Guoming Wang et al (Organic electronics.2014,15, 622-630) synthesized a series of novel single molecule electrochromic materials 2,4, 6-trisubstituted pyridine derivatives, and studied their electrochromic properties. Electrochromic devices were found to have longer response times and poorer stability. Fu She Han et al (J.am.chem. Soc.2008,130,6,2073-2081) designed a series of organic ligands containing bidentate terpyridine ligands, and experiments demonstrated that terpyridine-based organic ligands have good photoelectric properties, but also suffer from the disadvantage of a relatively long response speed. In order to solve the problems, the triphenylamine structure and the terpyridine are combined on the same compound through Ullmann coupling, and other modification groups are introduced to enrich the structure of the organic ligand so as to optimize the electrochromic performance of the metal supermolecular polymer. Disclosure of Invention In view of the above, the present invention aims to provide a multidentate organic ligand containing triphenylamine-terpyridine structure, a metal supermolecular polymer, a polymer film and a preparation method thereof, the polydentate organic ligand provided by the invention is coordinated with metal ions to synthesize a series of metal-supermolecular polymer films, and has the advantages of short color-changing response time and high electrochromic performance. In order to achieve the above object, the present invention provides the following technical solutions: the invention provides a multidentate organic ligand containing triphenylamine-terpyridine structure, which has a structure shown in formula I: wherein R 1 is selected from one of the following structures: R 2 is selected from one of the following structures: the invention also provides a preparation method of the multidentate organic ligand according to the technical scheme, which comprises the following steps: (1) Under alkaline condition, 4-nitrobenzaldehyde and 2-acetyl pyridine are used as raw materials, and 4'- (4-nitrophenyl) -2,2':6', 2' -terpyridine is synthesized by a one-pot method; (2) Under