Switch-On Diketopyrrolopyrrole-Based Chemosensors for Cations Possessing Lewis Acid Character

For the first time diketopyrrolopyrroles (DPPs) have been synthesized directly from nitriles possessing (aza)crown ethers leading to macrocycle-dye hybrids. Depending on the nature of the linkage between DPP and macrocyclic ring, various coordination effects are found. The strong interaction of the cations possessing Lewis acid character such as Li⁺ , Mg²⁺ and Zn²⁺ with 2-aminopyridin-4-yl-DPPs, leading to a bathochromic shift of both emission and absorption, as well as to strong enhancement of fluorescence was rationalized in terms of strong binding of these cations to the N=C-NR₂ functionality. The same effect has been observed for protonation. Depending on the size and the structure of the macrocyclic ring the complexation of cations by aza-crown ethers plays an important but secondary role. The interaction of Na⁺ and K⁺ with 2-aminopyridin-4-yl-DPPs leads to moderate enhancement of fluorescence due to the aza-crown ethers binding. The very weak fluorescence of DPP bearing 2-dialkylamino-pyridine-4-yl substituents is due to the closely lying T₂ state and the resulting intersystem crossing.