Electron transfer
Most examples of chemosensors for ions, such as those of alkali metal ions (Li+, Na+, K+, etc.) and alkali earth metal ions (Mg2+, Ca2+, etc.) are designed so that the excited state of the fluorophore component of the chemosensor is quenched by an electron transfer when the sensor is not complexed to these ions. No emission is thus observed, and the sensor is sometimes referred to as being 'switched off'. By complexing the sensor with a cation, the conditions for electron transfer are altered so that the quenching process is blocked, and fluorescence emission is 'switched on'. The probability of PET is governed by the overall free energy of the system (the Gibbs free energy ΔG). The driving force for PET is represented by ΔGET, the overall changes in the free energy for the electron transfer can be estimated using the Rehm-Weller equation. Electron transfer is distance dependent and decreases with increasing spacer length. Quenching by electron transfer between uncharged species leads to the formation of a radical ion pair. This is sometimes referred to as being the primary electron transfer. The possible electron transfer, which takes place after the PET, is referred to as the 'secondary electron transfer'. Chelation Enhancement Quenching (CHEQ) is the opposite effect seen for CHEF. In CHEQ, a reduction is observed in fluorescent emission of the chemosensor in comparison to that seen the originally for the 'free' sensor upon host–guest formation. As electron transfer is directional, such systems have also been described by the PET principle, being described as an enhancement in PET from the receptor to the fluorophore with enhanced degree of quenching. Such an effect has been demonstrated for the sensing of anions such as carboxylates and fluorides.