Langmuir–Blodgett Films of Diketopyrrolopyrroles with Tunable Amphiphilicity

In this work, we present the formation of H- and J-aggregates of amphiphilic centrosymmetric diketopyrrolopyrroles containing aliphatic or aromatic amino groups. The inherent amphiphilicity of these dyes predestines their assembly at interfaces to form ordered supramolecular structures. In this work, we employed the Langmuir-Blodgett (LB) technique to generate, manipulate, and deposit such supramolecular structures. The aforementioned amines provide an additional means to control the formation of the supramolecular assemblies. In the resulting LB films, both H- and J-aggregates of the dyes can be realized, leading to very broad absorption spectra. In contrast to many reports on H- and J-aggregates, the interactions between the symmetric diketopyrrolopyrroles are controlled via interface assembly and π-stacking and not by dipolar interactions. We show that in the case of the aliphatic, but not for the aromatic amine functionalization, the usage of an acidic subphase enables the transition from H- to J-aggregate-dominated LB films via an increase in the surface pressure during deposition.