Rational Design of Hemicyanine Langmuir Monolayers by Cation-Induced Preorganization of Their Structure for Sensory Response Enhancement

This study takes a novel approach to the enhancement of receptor properties of thin-film sensors based on hemicyanine dyes with dithia-aza-crown-ionophoric moiety. By means of in situ UV–vis and X-ray reflectivity (XRR) measurements, it was revealed that the introduction of up to 0.25 mmol of Hg2+ under a preliminarily compressed monolayer, formed on pure water, does not lead to cation binding. This is due to the formation of “head-to-tail” aggregates (H-type), in which ionophoric group is blocked by the neighboring molecule. However, the presence of barium cations in the subphase under the forming Langmuir monolayer of the mentioned compound causes codirectional (head-to-head) orientation of chromoionophore fragments. This provides preorganization of a monolayer structure that facilitates the binding of complementary mercury cations, even in a compressed state: asymmetric sandwich complexes containing two dye molecules coordinate a Hg2+ cation between them. This complex structure was confirmed by molecul...