Self-assembly of Acridine Orange into H-aggregates at the air/water interface: tuning of orientation of headgroup

The surface active derivative of the organic dye Acridine Orange (N-10-dodecyl-acridine orange (DAO)) has been included in mixed Langmuir monolayers with stearic acid (SA). The maximum relative content on DAO for a stable mixed monolayer is a molar ratio of X(DAO) = 0.5. Brewster angle microscopy (BAM) reveals a high homogeneity at the micrometer level for the mixed monolayer in equimolar proportion (X(DAO) = 0.5), whereas the appearance of domains occurs for lower content of DAO, i.e., X(DAO) = 0.2 and 0.1. The aggregation of the DAO headgroup leads to well-defined H-aggregates at the air/water interface for those mixed monolayers with a low content of DAO. However, for the mixed monolayers enriched in DAO, e.g., X(DAO) = 0.5, the molecular crowding prevents the formation of defined supramolecular structures. Molecular organization and tilting of the DAO headgroup is quantitatively analyzed by in situ UV-visible reflection spectroscopy. The formation of H-aggregates of the DAO headgroup can be reversibly tuned with the applied surface pressure. A molecular mechanism for the conformational rearrangement of the DAO molecule is proposed using RM1 quantum semiempirical calculations.