1,3,5-triarylpyrazolines - pH-driven off-on-off molecular logic devices based on a “receptor1-fluorophore-spacer-receptor2” format with internal charge transfer (ICT) and photoinduced electron transfer (PET) mechanisms

Abstract

The excited state photophysical properties of the 1,3,5-triarylpyrazolines 1–4 were studied in methanol and 1:1 (v/v) methanol–water, as well as 1:4 (v/v) methanol–water and water by fluorescence spectroscopy. The molecules 2–4 incorporate a “receptor1-fluorophore-spacer-receptor2” format while 1 is a reference compound based on a “fluorophore-receptor1” design. The molecular probes operate according to photoinduced electron transfer (PET) and internal charge transfer (ICT) processes. At basic and neutral pHs, 2–4 are essentially nonfluorescent due to PET from the electron-donating dimethylamino moiety appended on the 5-phenyl ring to the excited state of the 1,3,5-triarylpyrazoline fluorophore. At proton concentrations of 10−3 mol/L, the dimethylamino unit is protonated resulting in a strong blue fluorescence about 460 nm with significant quantum yields up to 0.54. At acid concentrations above 10−2 mol/L, fluorescence quenching is observed by an ICT mechanism due to protonation of the pyrazoline chromophore. Symmetrical off-on-off fluorescence–pH profiles are observed, spanning six log units with a narrow on window within three pH units. Hence, 2–4 are novel examples of ternary photonic pH sensing molecular devices.