Design,Synthesis And Anion Recognition Of Dithiophene Polypyrrole Macrocyclic Compounds

At present,photochromic materials have attracted much attention in the field of functional materials science.Dithiophene ethylene?DTE?derivatives should be one of the most popular photochromic materials due to their excellent thermal stability and remarkable fatigue resistance.The design,synthesis and application investigation in photoreceptor dyes,which possess photoisomeric function and can recognize specific objects,are the research direction of great concern.In particular,the response of receptor molecules to objects in the near-infrared region will make new contributions to many fields of life science,such as medical diagnosis or biological analysis.With this background,we expected to design and synthesis of novel photochemical anion recognition receptors.In this study,pyrrole and photoisomeric DTE,which are easy to form hydrogen bond with anions,are designed as the main components to syntheses purpose compounds,e.g.dipyrrole DTE chain compounds and tetrapyrrole DTE macrocyclic porphyrin derivatives.First of all,three chain compounds,i.e.DTEI,DTEP and DTEF,and two macrocyclic porphyrin derivatives,i.e.D₁P₄ and D₂P₈,were successfully synthesized from propionaldehyde,1-nitropropane,glacial acetic acid and methyl formate and so on.These compounds with pyrrole and thiophene perfluorocyclopentadiene as the basic skeleton structures and were characterized by UV-vis,MS and NMR.The main research results are as follows:1.Twenty intermediates and five target compounds have been synthesized.2.The photochromic property of DTEP is great.When nine common tetrabutylammonium salts are added individually to DTEP_closed in CH₂Cl₂,F^-and CN^-are selectively recognized with the redshifts from 625.5 nm to 728 nm or 692 nm.It has potential application value in the field of biology.And we further found that DTEP has the unique properties of photoisomerization with acid change.And we further explain the mechanism of anion recognition.3.To the best of our knowledge,D₁P₄ and D₂P₈ were synthesized for the first time by one-pot method.In CH₂Cl₂,compound D₁P₄ can recognize chloridion and bromine ion after acidification.