The Synthesis,Characterization,and Properties Of New BODIPY Dyes

BODIPYs have been widely applied in various fields,such as optical information storage,organic solar cells,organic semiconductor materials,photodynamic therapy and so on,owing to their unique optical and electronic properties.Accordingly,the designd and synthesis of new BODIPY dyes are of great important in current the research.In this thesis,we designed and synthesized new near-infrared BODIPYs and self-assembling BODIPYs bearing hydrogen-bonding groups.The properties of these new BODIPY dyes were investigated.The detailed research results are summarized as following:1.Seven new tetrathiophene-substituted BODIPY dyes were designed and synthesized by Stille cross coupling of 2,3,5,6-tetraiodinated BODIPY with different thiophene substituents respectively.The new compounds were characterized by ¹H NMR,¹³C NMR,HRMS,and IR spectroscopy.The single crystal structure of compound 4e was obtained by X-ray crystallography.Spectroscopic properties of seven tetrathiophene-substituted BODIPY dyes ware researched,and the research showed that absorption spectra of these dyes bathochromically shifted to near-infrared rigion by introducing thiophene moieties.Fluorescence quantum yield were tested in different sovlents,and the results showed that the fluorescence quantum yields were gradually decreased with the increase of polarity of solvent,which proved that fluorescence quenching may be caused by intramolecular charge transfer?ICT?processes.The electrochemical properties of the thienyl-functionalized BODIPYs have been investigated,and the electrochemical gaps of the BODIPYs were shown.The DFT calculation of the frontier molecular orbitals of these dyes corroborates the observed effects of peripheral substituents on the optical and redox properties.The electrochemical bandgaps of the BODIPY dyes were correlated with the optical bandgaps and calculated bandgaps,which proved that these dyes would be attractive for organic semiconductor materials.2.Seven new BODIPY dyes bearing uracil moities were designed and synthesized by Sonogashira cross coupling of 2,6-diiodinated BODIPY with5-ethynyl-1-n-octyluracil or 6-ethynyl-1-n-octyluracil.¹H-NMR,¹³C-NMR and HRMS were used to characterize the BODIPYs.The absorption spectra,fluorescence spectra,fluorescence quantum yield and fluorescence lifetime of these dyes in different solvent?dichloromethane,hexane,methylcyclohexane?were studied.The aggregation process of dyes 11-12 in hexane and methylcyclohexane were further monitored by temperature-and concentration-dependent UV/Vis absorption spectra.It was found that the lifetime of aggregates were shorter than that of monomer,and the fluorescence quantum yield of aggregates were increased characteristic for J-aggregates.3.Three new near-infrared aza-BODIPY dyes and four BODIPYs bearing3,5-distyryl substituents were designed and synthesized.The new dyes were characterized by ¹H-NMR,¹³C-NMR and HRMS,whose optical and electronic properties were studied.Three new tetradodecyloxy-substituted aza-BODIPY dyes were designed and synthesized.The absorption spectra and fluorescence spectra of these dyes were studied.The results showed that absorption spectra of these aza-BODIPY dyes shifted to near-infrared rigion,and fluorescence decayed with double exponential curve.The electrochemical properties of these aza-BODIPYs have been investigated,and electrochemical bandgaps were observed.New3,5-distyryl-substituted BODIPY derivatives were synthesized via Knoevenagel condensationreactionsof1,3,5,7-tetramethyl-BODIPYdyeswith p-methylbenzaldehyde or p-N,N-dimethylbenzaldehyde.The spectral and electrochemical properties of the 3,5-distyryl-substituted BODIPY dyes were studied,and electrochemical bandgaps were measured.The results proved that the bandgaps of aza-BODIPY dyes and 3,5-distyryl-substituted BODIPY dyes meet the requirement of solar cell materials.So,these new BODIOY dyes would be attractive for organic semiconductor materials.