Synthesis and Properties of Triphenylamine-containing Asymmetrical Perylene Diimides.
Kong Lushi, Tian Guofeng, Li Feng, Qi Shengli*, Wu Dezhen.
Chem.J. Chinese U., 2015, 36(12):2409-14.
【摘要】Two asymmetrical perylene diimides with triphenylamine structure,N-( 2-ethylhexyl)-N'-( 4-triphenylamine)-3,4,9,10-perylene diimide( PDI-ATPA) and 4,4',4''-tri[N-( 2-ethylhexyl)-3,4,9,10-perylene diimide]-triphenylamine( PDI-TATPA),were designed and synthesized,using branched alkyl chain substituted asymmetrical perylene monoanhydride monoimide( As PDA-Ⅰ) as the electron-accepting species and different functional triphenylamines,4-aminotriphenylamine( ATPA) and 4,4',4''-triaminotriphenylamine( TATPA),as the electron-donating moieties,respectively. The chemical structures were characterized by proton nuclear magnetic resonance(1H NMR),Infrared( IR) spectra and elemental ****ysis. The optical properties and aggregation behavior in solution were investigated by UV-Vis absorption and fluorescence emission spectra. Besides,molecular simulations were carried out to elucidate the molecular orbitals,energy levels and dipole moments of two asymmetrical perylene diimides. The results demonstrated that introducing the triphenylamine structure at the imide nitrogen of perylene diimide not only broadens the photo absorption region of perylene diimide but also has no effect on the absorption properties of the perylene core because of nodes in the highes occupied molecular orbital( HOMO) and lowest unoccupied molecular orbital( LUMO) at the imide nitrogen. Photoinduced electron transfer( PET) process take place from the eletron-donating moieties-ATPA and TATPA to the electron-accepting unit-perylene core,which has been confirmed by molecular simulations and lead to the fluorescence quenching. PDI-TATPA showed a star-shaped structure with highly regularity,which has been proven by the simulation data of dipole moment and has caused the self-assembly behavior easily occur in solution. Due to the self-assembly behavior,there are some differences between the UV-Vis spectra of PDI-ATPA and that of PDI-TATPA.
