Impact of the Acceptor Group on the Properties of Triphenylamine-Donor-Acceptor Dyes: An Experimental and Computational Study

Abstract

Three triphenylamine-Indane donor-acceptor dyes with different functional groups on the acceptor were studied to investigate how substitution would affect the optical properties. The dyes studied were IndCN, containing two malononitrile groups; InO, with two ketone groups; and InOCN, which features mixed functional groups. A combination of Raman spectroscopy, UV-vis absorption and emission spectroscopy, and density functional theory (DFT) calculations were employed for characterization. The dyes exhibited intramolecular charge transfer transitions with relatively high molar absorptivity (ϵabs) of ∼50 mM-1 cm-1 at 491-591 nm within the visible spectrum and emissions at 690-840 nm in dichloromethane. The malononitrile-containing dyes showed lower-energy absorption and emissions due to a reduced band gap compared to ketone-containing dyes. The bulkiness of the malononitrile group led to a bent geometry, increasing nonradiative decay and reducing the fluorescence quantum yield. The dyes exhibited fluorescence quantum yields less than 0.25 and lifetimes of ∼5 ns. Resonance Raman spectra and DFT calculations showed that the longer linker group (propen-1-ylidene linker) in these systems reduced the charge-transfer character of the optical transition. The emission intensities of the three dyes were temperature-sensitive, with ketone-containing dyes showing shifts in emission bands as well. This could be due to molecular stacking and intermolecular π-interactions.