N‐Protonation as a Switch of the Twisted Excited States with ππ* or nπ* Character and Correlation with the π‐Electrons Characteristic of Rotatable Bonds

Abstract

AbstractN‐protonation for numerous fluorophores is widely known as an efficient switch for the fluorescence turn‐on/off in acidic conditions, which has been applied in various scenarios that involve pH monitoring. Yet the universal mechanism for fluorescence regulation through N‐protonation is still elusive. Herein, the excited state deactivation processes are systematically investigated for a series of nitrogen‐containing fluorescent probes through theoretical approaches. Two types of mechanisms for the complex fluorescent phenomena by N‐protonation are concluded: one is through the regulation for the transition to a ππ* twisted intramolecular charge transfer (TICT) state; the other one applies for the case when nonradiative decay pathway is predominant by a dark nπ* state, which is also accompanied by an evident structural twisting and can be regarded as another kind of TICT state. More generally, the formation of the TICT state is closely related to the conjugated π‐electrons on the single bond that links the acceptor and donor part of fluorophores, which provides a simple strategy for evaluating the occurrence of the TICT process. The current contributions can bring novel insights for the rational design of functional fluorophores that involve TICT process in the excited states.