Construction Of Artificial Light Harvesting System Based On AIE-type Supramolecular Self-assembled Metal Ge

With the large amount of energy consumption,the development of new energy has become an important subject in the scientific community.Because of the advantages of solar energy being efficient and reusable,scientists have done a lot of research on it.The preparation of efficient light-harvesting systems is of great significance for simulating plant photosynthesis and exploring new green and clean energy.In recent years,there are more and more reports about artificial light-harvesting systems,but many published artificial light-harvesting systems are based on solution state.However,the practical application of most luminous materials depends on the solid state rather than the solution state,so the gel materials have great potential.Since the most significant advantage of aggregation-induced emission（AIE）materials is the high efficiency luminescence in the aggregation state,it is of great significance to construct the gel state artificial light-harvesting systems with AIE effect.In addition,the introduction of metal ions can regulate the fluorescence intensity and luminous range of the compound,so as to better construct the artificial light-harvesting systems.So far,few artificial light-harvesting systems based on metallogels have been reported.Therefore,it is still a difficult task to design and prepare excellent artificial light-harvesting systems based on metallogels with AIE effect.In this paper,three compounds were designed and synthesized to construct artificial light-harvesting system.This article is divided into the following parts:The first part mainly introduces the related content of supramolecular metallogels and AIE effect,and summarizes the related content of artificial light-harvesting system.According to the types of fluorescence chromophores,artificial light-harvesting systems can be divided into AIE type and non-AIE type,and introduces the research status of these two kinds of light-harvesting systems.Based on the research results at home and abroad and the work foundation of this research group,put forward their own research topic.In the second part,the functionalized acylhydrazone P1 was designed and synthesized.Compound P1 cannot self-assemble into supramolecular gel,but it can form supramolecular metallogel with Al³⁺in the mixed system of 1-propanol/H₂O（1:2,V/V）.P1-Al³⁺-gel formed by hydrogen bonding,π-πstacking interaction and metal coordination bond has strong AIE effect.Using P1-Al³⁺coordination system as energy donor,fluorescent dyes acridine yellow and acridine orange as energy acceptors,two kinds of gel state artificial light-harvesting systems were successfully constructed.In the third part,the Schiff-base small molecule compound P2 was designed and synthesized.The fluorescence intensity was enhanced significantly（about 138 times）by adding Al³⁺into the dimethyl sulfoxide（DMSO）solution of P2.In addition,P2-B-gel with strong AIE effect was formed in the mixed system of DMSO/H₂O using1,3:2,4-dibenzylidene sorbitol（B）as the carrier(V_{BD（DMSO solution containing B）}:V_D:V_water=1:1:2),and the supramolecular multicomponent metallogel was formed with Al³⁺.Using P2-Al³⁺coordination system as energy donor,Rhodamine B（Rh B）and Rhodamine 6G（Rh6G）as energy acceptors,two kinds of gel state artificial light-harvesting systems were successfully constructed.In the fourth part,the bi-benzimidazole derivative P3 was designed and synthesized.When common metal ions were added to the ethylene glycol solution of P3,only Al³⁺achieved a 49 nm redshift,and the selective detection of Al³⁺was achieved by compound P3.In addition,P3 can self-assemble into supramolecular gel with thermoreversible effect in ethylene glycol,and can form supramolecular metallogel with AIE effect with Al³⁺.Using P3-Al³⁺coordination system as energy donor,fluorescent dyes BODIPY 505/515（BDP）and Rh6G as energy acceptors,two kinds of gel state artificial light-harvesting systems were successfully constructed.