Synthesis and Electrochemical and Photophysical Properties of Azaterrylene Derivatives.

A series of terrylene derivatives, such as monoazaterrylene (MATerry), 1,6-diazaterrylene (DiATerry) and pristine terrylene (Terry), were synthesized by changing the number of nitrogen atoms at the bay region (1 and 6 positions of the Terry core). The electrochemical measurements suggested that the first one-electron reduction and oxidation potentials became positively shifted with increasing numbers of nitrogen atoms. This agreed with the energies of the corresponding highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) states estimated by DFT methods. In contrast, the HOMO-LUMO gaps approximately remained constant. This trend is quite similar to the spectroscopic behaviors observed by absorption and fluorescence spectra. The solvent polarity-dependent spectroscopic trends of DiATerry suggested the intramolecular charge-transfer (ICT) characters. The evaluation of the excited-state dynamics in various solvents indicated the electronic configurational changes of the excited states relative to the ground state via the ICT. This was supported by the Lippert-Mataga plots. Finally, the reversible protonation and deprotonation processes were also observed.