Tuning photophysical properties of triphenylamine and aromatic cyano conjugate-based wavelength-shifting compounds by manipulating intramolecular charge transfer strength

A series of triphenylamine-based aromatic cyano compounds have been synthesized as red-emitting fluorophores with large Stokes shifts in both solution (>100nm in CHCl3) and solid state (>150 nm in film). Intramolecular charge transfer (ICT) properties of the synthesized compounds are examined using UV-Vis absorptions, photoluminescence measurements and solvatochromic studies. Our studies suggest that Stokes shifts of these compounds can be fine-tuned by manipulating the ICT strength between donor and acceptor with various electronic donating groups, and the largest Stokes shifts are typically associated with compounds that have the strong ICT characters. The observed spectroscopic properties of the compounds are consistent with theoretical calculations using density function theory (OFT) or time-dependent density function theory (TD-DFT). The calculations suggest that the ICT occurs from localized HOMO to localized LUMO with magnitudes of 60-80%. The relative quantum yields of these fluorophores in solution are various and highly solvent dependent. In solid state, the quantum yields of the compounds are significantly increased and some can reach to 0.40. (C) 2012 Elsevier B.V. All rights reserved.