Solvent effects on the intramolecular charge transfer excited state of 3CzClIPN: a broadband transient absorption study.

The prediction of solvent properties using molecular probes often relies on correlating steady-state absorption and fluorescence measurements, as well as determining absorption maxima and/or Stokes shifts. In this study, we employ femtosecond broadband transient absorption (fs-bb-TA) spectroscopy to investigate the spectroscopic behaviour of the intramolecular charge transfer (ICT) excited state of 3CzClIPN (2,4,6-tri(9-carbazol-9-yl)-5-chloroisophthalonitrile), a representative ICT organic molecule, in both aromatic and non-aromatic solvents. Unlike observations in non-aromatic media, fs-bb-TA spectra of 3CzClIPN in aromatic solvents exhibit enhanced spectral broadening that strongly correlates with the solvent's polarity. We hypothesise that this spectral broadening originates from a wider configurational energy landscape experienced by the positively charged carbazole Cz group, owing to the larger size and, consequently, reduced solvation effectiveness of aromatic solvent molecules.