Research On The Synthesis And Properties Of Double-Center BODIPY Dyes

The 4,4-difluoro-4-bora-3a,4a-diaza-s-indacenes,also known as BODIPYs have received significant interest due to their stable optical properties,high absorption coefficients,easy functionalization and high oxidation potential.In this thesis,the research progress of these dyes and their synthetic methods and applications were summarized in brief.In order to study the influence of different substituents on nuclear structure on photoelectric properties,we have designed and synthesized a series of BODIPY derivatives,and their photophysical and electrochemical properties have been investigated.Based on our previous research,we synthesized dipyrromethanes in high yields to obtain BODIPY dyes according to a mild protocol.The main contents are as follows:1.Four novel symmetrical 4,4?-Difluoro-4-bora-3a,4a-diaza-sindacene?BODIPY?derivatives were synthesized.These BODIPY derivatives had different donor or acceptor units as conjugate bridges,and the BODIPYs meso-positions were substituted by thiophene or benzene as the terminal groups.The results of absorption spectra confirmed that these BODIPYs had a characteristic absorption peak,and the conjugate bridges had little influence on the intramolecular charge-transfer?ICT?interaction when used as neither donors nor acceptors.On the other hand,meso-position substituents had a weak influence on the ICT interaction in the BODIPYs,and meso-position thiophene-substituted ones had raised more intensive ICT than the meso-position benzene-substituted ones.Both the absorption spectra and the cyclic voltammetry data indicated that BODIPYs with meso-thiophene substituents possessed a lower oxidation potential and a narrower band gap than those with meso-benzene ones.2.Nine novel of dipyrromethanes containing biphenyl,terphenyl,carbazole and triphenylethylene were designed and synthesized.The structures of all these newly synthesized compounds were identified by ¹H NMR,¹³C NMR and MALDI-TOF-MS.We have developed the method for the synthesis ofbis?dipyrromethanes?into a universalmethod:bis?dipyrromethanes?weresynthesizedthroughan InCl₃-catalyzed condensation reaction between dialdehydes and pyrrole,and pyrrole could be recovered by vacuum distillation.This method has manyadvantages,such as easy manipulation,convenient purification,high yield and so on.The success of the synthesis of pyrromethanes provided enough raw materials for the synthesis of BODIPY derivatives through one-step protocol method for our next reaserch work.