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Photochromic ligand, re(i) rectangular supramolecular complex, preparation method and application

A photochromic and supramolecular technology, which is applied in the direction of color-changing fluorescent materials, chemical instruments and methods, and compounds of group 7/17 elements of the periodic table, can solve the problems of no ultraviolet photochromic performance and no optical performance, etc.

Inactive Publication Date: 2021-05-11
SHANDONG NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The inventors of the present invention have found through research that the existing Re(I) supramolecular complexes have no adjustable optical properties, especially no ultraviolet photochromic properties, so it is difficult to apply Re(I) supramolecular complexes to photoinduced color-changing material

Method used

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  • Photochromic ligand, re(i) rectangular supramolecular complex, preparation method and application
  • Photochromic ligand, re(i) rectangular supramolecular complex, preparation method and application
  • Photochromic ligand, re(i) rectangular supramolecular complex, preparation method and application

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Embodiment approach

[0047] The third embodiment of the present invention provides a Re(I) rectangular supramolecular complex, the chemical structural formula of which is shown in 1,

[0048]

[0049] Experiments show that the Re(I) rectangular supramolecular complex formed by the above photochromic ligands still has photochromic properties under ultraviolet irradiation.

[0050] In one or more examples of this embodiment, the single crystal molecular formula of the Re(I) rectangular supramolecular complex is: C40 h 22 Cl 4 N 2 o 6 Re 2 S 2 , the chemical formula is [Re 2 (CO) 6 (C 34 h 22 Cl 2 N 2 S 2 )(μ 2 -Cl) 2 , crystallized in the monoclinic crystal system, belonging to the C2 / m space group.

[0051] In this series of embodiments, the single crystal contains four Re(I) centers with the same environment, the entire molecule is in a rectangular frame, the metal Re(I) centers are located at 4 vertices, and the two short sides are respectively composed of 4 μ 2 -Chlorine bridge...

Embodiment 1

[0061] 1. Preparation of photochromic ligand L

[0062] Intermediates S1 and S2 were prepared according to literature methods.

[0063] Preparation of intermediate S3

[0064] Intermediate S2 (4.0g, 10mmol) was dissolved in thionyl chloride (25ml, 95.2g, 0.8mol) and heated to reflux for 4 hours. A drying tube should be installed for this reaction to prevent moisture from entering the reaction system. After the reaction was completed, the unreacted thionyl chloride was distilled off, and then a solution of 2-chloro-5-methylthiophene (2.3ml, 21mmol) in dichloromethane (30ml) was added. The reaction solution was cooled to 0°C with an ice-water bath, and 3.3 g of anhydrous aluminum trichloride (25 mmol) was added in several portions. Stirring was continued at 0°C for 30 min, then warmed to room temperature and stirring continued overnight. After the reaction was completed, ice water was added to the reaction system to remove excess aluminum chloride. The organic phase was sepa...

Embodiment 2

[0080] The ligand L prepared in Example 1 was dissolved in methanol to prepare a concentration of 1.65×10 -5 The methanol solution of M, under 298K, adopts 313nm ultraviolet light, carries out ultraviolet-visible absorption spectrum and fluorescence emission spectrum measurement to the methanol solution before and after illumination, the result is as follows Figure 7 As shown in the left figure, before and after illumination, the absorption wavelength of ligand L has red-shifted, and a new absorption band appears in the visible light range of 500-600nm, which is consistent with the color change of the solution before and after illumination. As shown on the right, the fluorescence emission spectrum of Ligand L is quenched after UV irradiation. It shows that the structure of ligand L changes before and after ultraviolet irradiation, from an open-loop state to a closed-loop state.

[0081] The Re (I) rectangular supramolecular complex solution DMF prepared by embodiment 1 is pr...

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Abstract

The invention discloses a photochromic ligand, a Re(I) rectangular supramolecular complex, a preparation method and an application thereof. The photochromic ligand has a chemical structural formula as shown in L: chemical composition of a Re(I) rectangular supramolecular complex The structural formula is shown in 1, and both the ligand and the Re(I) rectangular supramolecular complex provided by the present invention have ultraviolet photochromic properties.

Description

technical field [0001] The invention relates to a photochromic ligand, a Re(I) rectangular supramolecular complex, a preparation method and an application. Background technique [0002] The information disclosed in this background section is only intended to increase the understanding of the general background of the present invention, and is not necessarily taken as an acknowledgment or any form of suggestion that the information constitutes the prior art already known to those skilled in the art. [0003] Supramolecular complexes composed of metal Re(I) centers and organic ligands containing electron-donating groups are bridged by self-assembly and have geometric configurations such as triangles, rectangles, squares, and triangular prisms. This type of compound not only has diverse structural features, but also has great application potential in various fields such as luminescence, molecular sensing, catalysis, and drug delivery. Generally, such complexes are composed of ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D409/14C07F13/00C09K9/02
CPCC07D409/14C07F13/005C09K9/02C09K2211/1029C09K2211/1092C09K2211/188
Inventor 靳国霞王腾马建平
Owner SHANDONG NORMAL UNIV
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