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CN-122011406-A - Photoelectric response type organic-inorganic hybrid complex, and preparation method and application thereof

CN122011406ACN 122011406 ACN122011406 ACN 122011406ACN-122011406-A

Abstract

The invention belongs to the technical field of photoelectric functional materials, and discloses a photoelectric response type organic-inorganic hybrid complex, wherein the chemical formula of the complex is C 30 H 36 ClEuN 2 O 17 S, and an asymmetric unit of the complex comprises a main ligand 1,1 '-bis (4-carboxyphenyl) -4,4' -bipyridine, an auxiliary ligand 2, 5-thiophene dicarboxylic acid, three coordination water molecules, one free chloride ion and six free water molecules, and each Eu 3+ is coordinated with two oxygen atoms from two different main ligands 1,1 '-bis (4-carboxyphenyl) -4,4' -bipyridine, three oxygen atoms of two auxiliary ligands 2, 5-thiophene dicarboxylic acid and three oxygen atoms of three water molecules to form an eight-coordinated dodecahedron. Under 365 nm ultraviolet light excitation, the complex realizes the conversion of the crystal color from yellow to green in 1 s, shows quick light response characteristic and has wide application prospect.

Inventors

  • LI MENGHUA
  • HE MENGTING
  • LIU JUNXIA

Assignees

  • 河南大学

Dates

Publication Date
20260512
Application Date
20260128

Claims (10)

  1. 1. An organic-inorganic hybrid complex with a chemical formula of C 30 H 36 ClEuN 2 O 17 S, belonging to an orthorhombic system, and a space group Pbca, wherein the unit cell parameters are a= 14.0395 (12) a, b= 17.8197 (10) a, c= 29.7330 (13) a, α=90 °, β=90 °, γ=90°, and the asymmetric unit comprises one main ligand 1,1 '-bis (4-carboxyphenyl) -4,4' -bipyridine, one auxiliary ligand 2, 5-thiophene dicarboxylic acid, three coordinated water molecules, one free chloride ion, and six free water molecules, and each Eu 3+ coordinates with two oxygen atoms from two different main ligands 1,1 '-bis (4-carboxyphenyl) -4,4' -bipyridine, three oxygen atoms of two auxiliary ligands 2, 5-thiophene dicarboxylic acid, and three oxygen atoms of three water molecules to form an octa-dodecahedron; the three-dimensional structure is constructed by alternately connecting metal Eu 3+ with adjacent 1,1 '-bis (4-carboxyphenyl) -4,4' -bipyridine and 2, 5-thiophene dicarboxylic acid to form a one-dimensional chain structure, connecting the adjacent one-dimensional chain structures through 2, 5-thiophene dicarboxylic acid of another molecule to form a two-dimensional network structure, connecting the adjacent two-dimensional network structures through 1,1 '-bis (4-carboxyphenyl) -4,4' -bipyridine to form a three-dimensional hole frame structure, and connecting chloride ions with the three-dimensional hole frame structure through hydrogen bonds.
  2. 2. An opto-electronically responsive organic-inorganic hybrid complex according to claim 1, wherein the complex achieves a transition from yellow to green in crystal color within 1 s upon excitation by 365 nm uv light.
  3. 3. An opto-electronically responsive organic-inorganic hybrid complex according to claim 1, wherein said complex exhibits bright orange-red fluorescence upon exposure to ultraviolet light at 365 nm and exhibits reduced but non-quenching fluorescence intensity upon exposure to ultraviolet light.
  4. 4. The preparation method of the photoelectric response type organic-inorganic hybrid complex according to any one of claims 1-3 is characterized by comprising the following steps of uniformly mixing europium salt, 1' -bis (4-carboxyphenyl) -4,4' -bipyridine, 2, 5-thiophene dicarboxylic acid, water, N ' -dimethylacetamide, acetonitrile and dilute hydrochloric acid, and reacting to obtain yellow diamond crystals.
  5. 5. The method for preparing an organic-inorganic hybrid complex according to claim 4, wherein the europium salt is europium nitrate hexahydrate.
  6. 6. The method for preparing a photoelectric-responsive organic-inorganic hybrid complex according to claim 4, wherein the mass ratio of europium salt, 1 '-bis (4-carboxyphenyl) -4,4' -bipyridine and 2, 5-thiophenedicarboxylic acid is 7:3:2.
  7. 7. The method for preparing an organic-inorganic hybrid complex according to claim 4, wherein the volume ratio of water, N' -dimethylacetamide, acetonitrile and dilute hydrochloric acid is 10:10:40:1.
  8. 8. The method for preparing an organic-inorganic hybrid complex according to claim 4, wherein the reaction temperature is 120 ℃ and the reaction time is 24-72 h.
  9. 9. Use of the opto-electrically responsive organic-inorganic hybrid complex according to any one of claims 1 to 3 in opto-electrochromic articles.
  10. 10. The use of the opto-electronic response type organic-inorganic hybrid complex according to any one of claims 1 to 3 in ultraviolet detection products.

Description

Photoelectric response type organic-inorganic hybrid complex, and preparation method and application thereof Technical Field The invention belongs to the technical field of photoelectric functional materials, and relates to a photoelectric response type organic-inorganic hybrid complex, a preparation method and application thereof. Background Photochromic compounds are a class of smart materials that undergo a reversible change in color or optical properties under specific wavelength illumination. Such changes are typically driven by photoinitiated molecular structure changes or electronic state adjustments. When the light source is removed or the lighting conditions are changed, the material may revert to its original shape. Because of the characteristics of quick response and high fatigue tolerance, the material has great development potential in the front technical fields of automobile industry, molecular switches, ray detection, biological imaging and the like. Electrochromic compounds refer to optical changes in transmittance or reflectance that are reversible under an externally applied voltage. Electrochromic devices are receiving wide attention in the fields of smart windows, sensing, and display, due to their unique adjustable optical properties. In recent years, a number of novel photochromic materials have emerged, particularly stimulus-responsive viologen composites. They have not only the photochromic properties of the viologen compound itself, but also by complexing with other materials, realizes the accurate regulation and control of the stimulus response and the optimization of the performance, thereby showing wide application prospect in a plurality of fields. The development of the material is relatively late, and the problems of single stimulus response, single application mode and slow response rate still exist in the current research of the photochromic material, so that the multifunctional response of the single material cannot be realized, and the multiple application requirements are difficult to meet at the same time. Disclosure of Invention Aiming at the technical problems of single stimulus response and slow response rate of the photochromic material, the invention provides the photoelectric response type organic-inorganic hybrid complex which can change from yellow to green in ultraviolet irradiation 1s, has rapid light response characteristic and has wide application prospect. In order to achieve the above purpose, the present invention adopts the following technical scheme: In a first aspect, the present invention provides an organic-inorganic hybrid complex 1 of the formula C 30H36ClEuN2O17 S, belonging to an orthorhombic system, the space group Pbca, the unit cell parameters a= 14.0395 (12) a, b= 17.8197 (10) a, c= 29.7330 (13) a, α=90 °, β=90 °, γ=90°, wherein the asymmetric unit comprises one main ligand 1,1 '-bis (4-carboxyphenyl) -4,4' -bipyridine, one auxiliary ligand 2, 5-thiophenedicarboxylic acid, three coordinating water molecules and one free chloride ion and six free water molecules, each Eu 3+ forming an octacoordinate dodecahedron with two oxygen atoms from two different main ligands 1,1 '-bis (4-carboxyphenyl) -4,4' -bipyridine, three oxygen atoms of two auxiliary ligands 2, 5-thiophenedicarboxylic acid and three oxygen atoms of three water molecules; the three-dimensional structure is constructed by alternately connecting metal Eu 3+ with adjacent 1,1 '-bis (4-carboxyphenyl) -4,4' -bipyridine and 2, 5-thiophene dicarboxylic acid to form a one-dimensional chain structure, connecting the adjacent one-dimensional chain structures through 2, 5-thiophene dicarboxylic acid of another molecule to form a two-dimensional network structure, connecting the adjacent two-dimensional network structures through 1,1 '-bis (4-carboxyphenyl) -4,4' -bipyridine to form a three-dimensional hole frame structure, the chloride ions are connected with the three-dimensional hole frame structure through hydrogen bonds. In the technical scheme, under the excitation of 365 nm ultraviolet light, the color of the complex 1 is converted from yellow to green in 1 s. In the above technical scheme, the complex 1 can show bright orange-red fluorescence when placed under dark condition after ultraviolet light excitation of 365 nm, and the fluorescence brightness is weakened but not quenched with the increase of ultraviolet light excitation time. The invention provides another photoelectric response type organic-inorganic hybrid complex 2, wherein the chemical formula of the complex 2 is C 30H36ClDyN2O17 S, the complex belongs to an orthorhombic system, a space group Pbca, and single cell parameters are a= 13.5832 (6) a, b= 17.7071 (6) a, c= 29.7043 (11) a, alpha=90, beta=90 and gamma=90 degrees, and an asymmetric unit of the complex comprises a main ligand 1,1 '-bis (4-carboxyphenyl) -4,4' -bipyridine, an auxiliary ligand 2, 5-thiophene dicarboxylic acid, three coordination water molecules, a free