CN-121988387-A - Light capturing system based on dicyanostilbene derivative and preparation method and application thereof

Abstract

The invention discloses a light capturing system based on dicyanostilbene derivative, and a preparation method and application thereof. The light capturing system takes a supermolecule nano aggregate formed by assembling a p-methylpyridinium modified dicyanostilbene derivative and polyacrylic acid through electrostatic action as a light capturing antenna and an energy donor, and takes fluorescent dye loaded on the supermolecule nano aggregate as an energy acceptor. The light capturing system provided by the invention has a wide color regulation range and remarkably enhances active oxygen (comprising 1 O 2 and O 2 ) • ) Generating capability. Under the condition of water phase, the light capturing antenna of the system can enhance the generation of ROS, and after fluorescent dye is loaded, the ROS is further enhanced.

Inventors

• XIAO TANGXIN
• LIANG TAO
• Dang Xiaoman
• WU KEHUI

Assignees

• 常州大学

Dates

Publication Date

20260508

Application Date

20260129

Claims (10)

1. 1. A light capturing system, characterized in that the light capturing system uses a supermolecule nano aggregate formed by assembling a p-picolinium modified dicyanostilbene derivative (DCSPy) and polyacrylic acid (PAA) through electrostatic action as a light capturing antenna and an energy donor, and uses a fluorescent dye loaded on the supermolecule nano aggregate as an energy acceptor; the chemical structure of the p-methylpyridinium salt modified dicyanostilbene derivative (DCSPy) is shown as a formula (I): Formula (I).
2. 2. The light capturing system of claim 1, wherein the polyacrylic acid has a chemical structure as shown in formula (II): Formula (II); Preferably, the average molecular weight of the polyacrylic acid is 2000-5000; Preferably, the fluorescent dye is rhodamine 6G (Rh 6G), and the chemical structure of the rhodamine 6G (Rh 6G) is shown as a formula (III): formula (III).
3. 3. The light capturing system of claim 1, wherein the p-methylpyridinium modified dicyanostilbene derivative (DCSPy) is electrostatically assembled with polyacrylic acid (PAA) in an aqueous solution to form supramolecular nanoclusters; Preferably, the mass ratio of the p-picolinium modified dicyanostilbene derivative (DCSPy) to polyacrylic acid (PAA) is 0.02-1100:1, preferably 0.36-15:1, more preferably 2-3:1; Preferably, the molar ratio of the p-methylpyridinium modified dicyanostilbene derivative (DCSPy) to the fluorescent dye is 50-800:1.
4. 4. A method of manufacturing a light harvesting system according to any one of claims 1-3, comprising the steps of: (1) Self-assembling a p-methylpyridinium modified dicyanostilbene compound (DCSPy) in water to obtain a DCSPy assembly; (2) Assembling DCSPy assembly and polyacrylic acid in water to obtain a supermolecule nano aggregate; (3) And carrying out ultrasonic treatment on the supermolecule nano aggregate and the fluorescent dye in water to obtain the light capturing system.
5. 5. The preparation method according to claim 4, wherein the mass ratio of the p-methylpyridinium modified dicyanostilbene derivative (DCSPy) to polyacrylic acid (PAA) is 0.02-1100:1, preferably 0.36-15:1, more preferably 2-3:1; Preferably, the molar ratio of the p-methylpyridinium modified dicyanostilbene derivative (DCSPy) to the fluorescent dye is 50-800:1; preferably, in step (1), the concentration of the p-methylpyridinium modified dicyanostilbene compound in water is 4X 10 6 ~4×10 3 M is preferably 4X 10 5 M; Preferably, in step (2), the polyacrylic acid has a concentration of 2.75X10 in water 6 ~1.1×10 4 G/mL, preferably 1.1X10 5 g/mL。
6. 6. The method of claim 4, wherein in step (2), the assembling is performed under ultrasound.
7. 7. The method according to claim 4, wherein the method for producing the p-methylpyridinium-modified dicyanostilbene compound (DCSPy) comprises the steps of: S1) combining Compound 1 with Compound 2 is prepared by reflux under the action of alkali; The compound 1 is ; The compound 2 is ; X is a leaving group; s2) preparing the p-methylpyridinium modified dicyanostilbene compound (DCSPy) by the compound 2 and picoline under the reflux effect.
8. 8. The process according to claim 7, wherein in step S1), the compound 1 is mixed with The molar ratio of (2) is 1:5-6; Preferably, the X is-Br, -Cl or p-toluenesulfonyl (OTs); preferably, the base is potassium carbonate, magnesium carbonate or sodium carbonate; Preferably, the refluxing is performed in acetone or acetonitrile; Preferably, the reflow time is 48-72 hours.
9. 9. The preparation method according to claim 7, wherein in the step S2), the molar ratio of the compound 2 to picoline is 1:16-18; Preferably, the refluxing is performed in tetrahydrofuran or anhydrous dichloromethane; Preferably, the reflow time is 48-98 h.
10. 10. Use of a light-harvesting system according to any of claims 1-3 or a method of preparation according to any of claims 4-9 for the preparation of luminescent materials, optoelectronic devices, photocatalysts.

Description

Light capturing system based on dicyanostilbene derivative and preparation method and application thereof Technical Field The invention belongs to the technical field of organic light-emitting catalytic materials, and particularly relates to a light capturing system based on dicyanostilbene derivatives, and a preparation method and application thereof. Background Along with the increasing severity of environmental pollution problems and the continuous deepening of green and sustainable synthesis concepts, the development of efficient, controllable and environment-friendly photocatalytic materials has become a research hotspot in the fields of material science and organic synthesis. The photocatalysis technology has wide application prospect in aspects of organic synthesis, energy conversion and the like by converting light energy into chemical energy to drive a reaction process. Compared with the traditional catalytic system, the photocatalysis generally has the advantages of mild reaction conditions, low energy consumption, environmental friendliness and the like, so that the photocatalysis has important significance in promoting the development of green chemistry. The Light capturing system (Light-HARVESTING SYSTEM, LHS) is used as a core component in the photocatalytic system, and the structural design and the energy transfer efficiency directly determine the efficiency and the selectivity of the photocatalytic process. LHS in nature relies on orderly arranged antenna molecules to achieve efficient light energy capture and transmission through energy resonance transfer, which provides important elicitations for the design of artificial light capture systems. In recent years, researchers construct supermolecule photocatalytic materials with good photoresponsive properties through strategies such as interaction between a host and a guest, non-covalent bond assembly and the like, which benefit from development of supermolecule chemistry. The material generally has highly adjustable luminescence property and structural flexibility, and can self-assemble to form a stable nano structure in complex environments such as water phase and the like, thereby improving photocatalysis efficiency. The photocatalyst in the prior art is mostly based on a hydrophobic conjugated framework, so that the solubility of the photocatalyst in water is poor, and the application of the photocatalyst in a green reaction system is limited. With the development of various novel water-soluble host and guest materials, the construction of stable, tunable, and environmentally friendly light capturing systems has become an important development direction. Disclosure of Invention Aiming at the technical problems, the invention provides a light capturing system based on dicyanostilbene derivatives, and a preparation method and application thereof. The invention assembles the p-picolinium modified dicyanostilbene derivative (DCSPy) and polyacrylic acid (PAA) in water solution through electrostatic action to obtain DCSPy-PAA supermolecule nano aggregate, takes the supermolecule nano aggregate as a light capturing antenna and an energy donor, and loads fluorescent dye to obtain the light capturing system. The PAA can be assembled with the p-picolinium modified dicyanostilbene derivative, and during the assembly process, fluorescence of opening DCSPy and generation of Reactive Oxygen Species (ROS) are enhanced, and after fluorescent dye is loaded, along with further enhancement of the ROS, the two synergistically promote efficient energy capture and transmission. In order to achieve the above purpose, the present invention adopts the following technical scheme: In one aspect, the present invention provides a light harvesting system using a supramolecular nano-aggregate formed by assembling a p-methylpyridinium modified dicyanostilbene derivative (DCSPy) and polyacrylic acid (PAA) through electrostatic action as a light harvesting antenna and an energy donor, and using a fluorescent dye loaded on the supramolecular nano-aggregate as an energy acceptor; the chemical structure of the p-methylpyridinium salt modified dicyanostilbene derivative (DCSPy) is shown as a formula (I): Formula (I). In the technical scheme of the invention, the chemical structure of the polyacrylic acid is shown as a formula (II): Formula (II); preferably, the average molecular weight of the polyacrylic acid is 2000-5000. Preferably, the fluorescent dye is rhodamine 6G (Rh 6G), and the chemical structure of the rhodamine 6G (Rh 6G) is shown as a formula (III): formula (III). As a preferred embodiment, the p-methylpyridinium modified dicyanostilbene derivative (DCSPy) is electrostatically assembled with polyacrylic acid (PAA) in an aqueous solution to form supramolecular nanoclusters; Preferably, the mass ratio of the p-picolinium modified dicyanostilbene derivative (DCSPy) to polyacrylic acid (PAA) is 0.02-1100:1, preferably 0.36-15:1, more preferably 2-3:1; Preferably, the