Intermolecular Charge-Transfer Luminescence by Self-Assembly of Pyridinium Luminophores in Solutions

Designing a luminophore for application both in solution and in the solid state is a highly challenging task given the distinct nature of intermolecular interactions in these phases. In this context, we demonstrate that self-assembly of non-emissive charged pyridinium luminophores enables luminescence in solutions through a mechanism that is characteristic for the crystal state. Specifically, protonation of pyridine luminophore subunits in a solution promotes oligomer formation through intermolecular π⁺ -π interactions, leading to an intermolecular charge-transfer type luminescence. The luminescence turn-on by protonation is utilized for a highly efficient solution-state luminescent sensing of hydrogen chloride and sulfonic acids (TfOH, TsOH and MsOH) with detection limits spanning the range from 0.06 to 0.33 ppm. The protonation followed by self-assembly results in a bathochromic shift of the emission from 420 nm to 550 nm.