Linear dyes are molecular mimics of dipole antennas that receive UV–vis light. In this work the assembly of linear dyes via the Langmuir technique to achieve uniform dye alignment for optically anisotropic molecular dipole antenna arrays is presented. The molecular orientations in these arrays are quantified from Langmuir isotherms, topography data, and from polarization‐ and angle‐dependent UV–vis transmission spectra. It is achieved the smallest angles by which the transition dipole moment orientation deviates from vertical alignment (16°–30°) in the antenna arrays that have been reported in literature so far. The resulting maximum absorption contrast between grazing and vertical incidence amounts to 75%. This high optical anisotropy enables application as anisotropic receiver arrays in optical communication, as optical layers for privacy applications, or other applications building on dichroic dye layers.
Supramolecular dye structures, which are often ruled by π−π interactions between planar chromophores, crucially determine the optoelectronic properties of layers and interfaces. Here, we present the interfacial assembly of perylene monoanhydride and monoimide that do not feature a planar chromophore but contain chlorine substituents in the bay positions to yield twisted chromophores and hence modified π-stacking. The assembly of the twisted perylene monoanhydride and monoimide is driven by their amphiphilicity that ensures proper Langmuir layer formation. The shielding of the hydrophilic segment upon attaching an alkyl chain to the imide moiety yielded a more rigid Langmuir layer, even though the degrees of freedom were increased due to this modification. For the characterization of the Langmuir layer's supramolecular structure, the layers were deposited onto glass, silver, and gold substrates via Langmuir−Blodgett (LB) and Langmuir−Schaefer (LS) techniques and were investigated with atomic force microscopy and surface-enhanced resonance Raman spectroscopy (SERRS). From the similarity between all SERR spectra of the LS and LB layers, we concluded that the perylenes have changed their orientation upon LB deposition to bind to the silver surface of the SERRS substrate via sulfur atoms. In the Langmuir layer, the perylenes, which are πstacked with half of the twisted chromophores, must already be inclined and cannot achieve full parallel alignment because of the twisting-induced steric hindrance. However, upon rotation, the energetically most favorable antiparallel aligned structures can be formed and bind to the SERRS substrate. Thus, we present, to the best of our knowledge, the first fabrication of quasi-twodimensional films from twisted amphiphilic perylene monoimides and their reassembly during LB deposition. The relation between the molecular structure, supramolecular interfacial assembly, and its adoption during adsorption revealed here is crucial for the fabrication of defined functionalizations of metal surfaces, which is key to the development of organic (opto)electronic devices.
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