Fundamental photoluminescence properties of pyrene carbonyl compounds through absolute fluorescence quantum yield measurement and density functional theory

We reviewed the photophysical properties of carbonyl-functionalized pyrene derivatives [i.e., pyrene with aldehyde (PA: 1-formylpyrene), ketone (PK: 1-acetylpyrene), carboxylic acid (PCA: 1-pyrenecarboxylic acid), and ester groups (PE: 1-methoxycarbonylpyrene)] using a measurement of absolute fluorescence quantum yield in various solvents and time-dependent density functional theory (TD-DFT) calculations. Here, we obtained new important data that fill in the gaps in existing datasets on these properties and help identify photoluminescence mechanisms. The results of the TD-DFT calculations were in agreement with the experimental results, and indicated that the low fluorescence of PA and PK is derived not only from intersystem crossing but also from internal conversion due to the proximity effect; this inference was also supported by the measurements of the photoluminescence spectra at low temperatures. In addition, factors leading efficiently to non-radiative processes were shown to be absent in PCA and PE. Thus, we successfully revised and systematized the photophysical properties of pyrene modified by carbonyl substitutes, including carboxamide groups, which were previously reported by us. Moreover, we showed that the photoluminescence properties of such compounds might be predictable by using TD-DFT calculations.