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Spotlight on Excitonic Coupling in Polymorphic and Textured Anilino Squaraine Thin Films

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journal contribution
posted on 23.10.2017, 00:00 by Frank Balzer, Heiko Kollmann, Matthias Schulz, Gregor Schnakenburg, Arne Lützen, Marc Schmidtmann, Christoph Lienau, Martin Silies, Manuela Schiek
Structural diffraction analysis of an anilino squaraine with branched isobutyl side chains shows crystallization into two polymorphic structures in the bulk and in spin-casted thin films. We observe multipeaked and pleochroic absorption spectra being blue-(red)-shifted for the monoclinic (orthorhombic) polymorph. We understand the packing as Coulombic molecular H-(J)-aggregates supporting Davydov splitting. Pictures of projected Davydov components in oriented thin films fit well to polarization resolved spectro-microscopy and crossed-polarized light microscopy investigations. By comparison with literature on anilino squaraines with linear alkyl side chains, we point out a general trend for steering the thin film excitonic properties by simple side chain and/or processing condition variation. Combined with the ability to locally probe the direction of transition dipole moments, this adds value to the rational design of functional thin films for optoelectronic applications, especially envisioning ultrastrong light–matter interactions.