Synthesis Of Several Asymmetrical Perylene Derivatives And Selective Recognition Of Fluoride

Perylene derivatives are synthesized from economical starting materials,have rigid planar backbones,large absorption cross-section,outstanding thermal and photochemical stability,high fluorescence quantum yields,low photobleaching yields,high charge-carrier mobility,all factors that make them well suited to adaptation as promising active elements in organic photoelectrical devices and biological fields.Among all members of the perylene derivatives family,perylene diimides?PDIs?derivatives have attracted more attention,because of their facile synthesis.However,many PDIs display poor solubility and thus show very weak fluorescence owing to the aggregation of perylene chromophores,which is a disadvantage that limits their applications,especially in biological field.The perylene tetra-?alkoxycarbonyl?derivative,which is structurally related to PDIs,is more soluble in organic solvents and show excellent fluorescence.The results can provide guidance for the designandsynthesisofnewkindoffluorescentperylene tetra-?alkoxycarbonyl?derivatives and is expected to pave the way towards new applications.According to the current research of perylene derivative and our previous works,this thesis developed several novel pyran-annulated perylene diimides and a perylene tetra-?alkoxycarbonyl?derivative substituted with amino and hydroxyl at the same side.Based on those novel perylene derivatives,seven fluorescent probes were synthesized and were also used as colorimetric and fluorescent probe for fluoride ion detection with remarkable selectivity.The main contents are as follows:1?Facile syntheses,characterization,and physical properties of sulfur-decorated pyran-annulated perylene diimides.Three sulfur-containing pyran-annulated perylene diimides?PDIs?were synthesized from commercially available PDIs through a nucleophilic substitution/cyclizationreactionsequence.Theirphotophysical properties were strongly affected owing to the pyran-annulation and substitution of sulfur-containing units in the bay positions.The compounds were fully characterized by¹H and¹³C NMR,and FT-IR spectroscopy,as well as HRMS and TGA.The PDI derivatives exhibited significantly narrow HOMO–LUMO band gaps,high photochemical and thermal stability and excellent solubility in common organic solvent.Moreover,these materials exhibited quite different absorptions and emissions in dichloromethane,which contained almost visible region and were in agreement with the DFT-calculated results.2?Novel hydroxyl-substituted or amino-substituted Perylene-3,4,9,10-tetracarboxylic acid diimides for selective recognition of fluorideSeveral novel highly fluorescent sensors to F^-based on PDIs were designed and efficiently synthesized.The physical properties of the compounds had been fully studied.All receptors have shown no affinity for other anions.Upon addition of F^-anion to their DCM solution,dramatic color change and fluorescence quenching were observed.Furthermore,the red-shift of the absorption decreases the effect of background owing to the annulation of the pyran structure to perylene bay area.3?Facile syntheses,characterization,and physical properties of two kinds of dimer based on pyran-annulated perylene diimides.Twokindsofdimerwerefacilelysynthesizedfrom monobromo-substituted pyran-annulated perylene diimides?PDIs?through C-C coupling.The dimers were fully characterized by¹H NMR,¹³C NMR,FT-IR,HRMS.Two dimers exhibited similar Uv-vis spectra,fluorescence spectra,HOMO-LUMO bandgaps and high photochemical and thermal stability.Horeover,these materials exhibited different cyclic voltammetry curves in dichloromethane solutions,besides dihedral angle between their perylene cores.This difference should be owing to their different imide group.4?Synthesis of 1-amino-12-hydroxyl-perylene tetra-?alkoxycarbonyl?for selective sensing of fluoride and photocatalytically splitting of water into hydrogenA perylene tetra-?alkoxycarbonyl?derivative substituted with amino and hydroxyl at the same side was synthesized through an intramolecular rearrangement mechanism.The properties of it were detected by absorption,fluorescencespectraandelectrochemical response.1-amino-12-hydroxyl-perylene tetra-?alkoxycarbonyl?was used as colorimetric and fluorescent probe for fluoride ion detection with remarkableselectivity.Furthermore,thenewperylene tetra-?alkoxycarbonyl?derivatives could be used as catalyst to photocatalytically splitting of water into hydrogen.