A fluorescent molecular rotor showing vapochromism, aggregation-induced emission, and environmental sensing in living cells

Abstract

Among the plethora of recently proposed molecular sensors, those belonging to the class of fluorescent molecular rotors (FMRs) have attracted much attention owing to their peculiar photophysical properties that enable an unprecedented sensitivity towards environmental microviscosity. The usual FMR synthetic design prescribes chromophores characterized by an intramolecular rotation between two well-defined excited states, a locally excited state and a twisted internal charge transfer (TICT) state, where the sensing capabilities arise from a dual competition of the corresponding radiative/non-radiative decay processes. However, we have recently demonstrated a different modus operandi of a new subclass of solvatochromic FMRs, which exploit a solvent-independent, barrier-free intramolecular rotation of the excited dye. The rotational dynamics is modulated by local viscosity and, in turn, manifested through a variable spectral signal. In order to translate the same rotational mechanism in a versatile sensor of polarity and viscosity, we designed and thoroughly characterized a novel FMR, namely 4-(triphenylamino)-phthalonitrile (TPAP). Remarkably, in addition to a high sensitivity versus solvent polarity and viscosity, TPAP is also able to form stable fluorescent nanoparticles characterized by aggregation-induced emission, via a simple sonochemical treatment. Such peculiar features are tested in different applications aiming at illustrating its capability to report on solvatochromic and vapochromic effects, as well as to provide detailed intracellular information through bioimaging studies.