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An enantiomerically pure (R)-2-methylpyrrolidine-based anilino squaraine crystallizes in two chiral polymorphs adopting a monoclinic C2 and an orthorhombic P2(1)2(1)2(1) structure, respectively. By various thin-film preparation techniques, a control of the polymorph formation is targeted. The local texture of the resulting textured thin films is connected to the corresponding optical properties. Special attention is paid to an unusual Davydov splitting, the anisotropic chiroptical response arising from preferred out-of-plane orientation of the crystallites, and the impact of the polymorph specific excitonic coupling.

Solution-processed and thermally annealed thin films from a series of n-alkyl terminated anilino squaraines are systematically investigated regarding their structural and optical properties by means of X-ray diffraction (XRD) and spectroscopic ellipsometry (SE). Their characteristic intense double-hump-shaped absorbance spectra consisting of coupled H-aggregate and intermolecular charge transfer (ICT) resonance bands make them appealing for fundamental light-matter interaction studies, and their environmental sustainability invites for consumer optoelectronic applications. Now, the single-crystal structure of the n-pentyl anilino squaraine (nPSQ) provides a missing link to identify potential odd-even effects with respect to the terminal alkyl chain for bulk crystals. While all single crystals adopt a triclinic unit cell with biaxial dielectric properties, the thin films condense into effectively uniaxial anisotropic thin films. Here, the inherently low sensitivity to the out-of-plane complex refractive index of SE in reflection is reasonably compensated by adding transmission SE and transmission intensity data. With that, a general picture of the structural and dielectric properties of n-alkyl anilino squaraine thin films is launched, revealing that the terminal alkyl chain length affects the structural and optical properties in a twofold way: we observe a steady change which is superimposed by an anisotropic odd-even effect.

A facile route to soft matter self-powered bulk heterojunction photodiode detectors sensitive to the circular polarization state of light is shown based on the intrinsic excitonic circular dichroism of the photoactive layer blend. As light detecting materials, enantiopure semiconducting small molecular squaraine derivates of opposite handedness are employed. Via Mueller matrix ellipsometry, the circular dichroism is proven to be of H-type excitonic nature and not originating from mesoscopic structural ordering. Within the green spectral range, the photodiodes convert circular polarized light into a handedness-dependent photocurrent with a maximum dissymmetry factor of ±0.1 corresponding to 5% overall efficiency for the polarization discrimination under short circuit conditions. On the basis of transfer matrix optical simulations, it is rationalized that the optical dissymmetry fully translates into a photocurrent dissymmetry for ease of device design. Thereby, the photodiode's ability to efficiently distinguish between left and right circularly polarized light without the use of external optical elements and voltage bias is demonstrated. This allows a straightforward and sustainable future design of flexible, lightweight, and compact integrated platforms for chiroptical imaging and sensing.

As a step toward the realization of neuroprosthetics for vision restoration, we follow an electrophysiological patch-clamp approach to study the fundamental photoelectrical stimulation mechanism of neuronal model cells by an organic semiconductor−electrolyte interface. Our photoactive layer consisting of an anilino-squaraine donor blended with a fullerene acceptor is supporting the growth of the neuronal model cell line (N2A cells) without an adhesion layer on it and is not impairing cell viability. The transient photocurrent signal upon illumination from the semiconductor−electrolyte layer is able to trigger a passive response of the neuronal cells under physiological conditions via a capacitive coupling mechanism. We study the dynamics of the capacitive transmembrane currents by patch-clamp recordings and compare them to the dynamics of the photocurrent signal and its spectral responsivity. Furthermore, we characterize the morphology of the semiconductor−electrolyte interface by atomic force microscopy and study the stability of the interface in dark and under illuminated conditions.

The impact on chiral aggregation in solution processed and thermally annealed thin films of two indolenine and one anilino squaraines with chiral (S)-citronellyl functionalization at the nitrogen of the squaraine backbone is investigated. A pseudo polymorphic crystal structure is obtained for one of the indolenine squaraines, but thin films of both compounds are basically non-aggregated and truly isotropic as evidenced by spectroscopic ellipsometry. The anilino squaraine coalesces and readily aggregates to circular dichroic but discontinuous thin films. The extent of circular dichroism correlates with the morphology of the samples, which is quantified by Mueller matrix polarimetry in combination with atomic force microscopy. The shape of the CD spectra reinforces the hybrid Frenkel and charge-transfer excitonic nature of the characteristic double hump signatures within unpolarized absorbance spectra of previously investigated non-chiral anilino squaraines with linear alkyl chain functionalization. Such excitonic CD offers an additional design parameter for next-generation opto-electronic devices.

The impact on chiral aggregation in solution processed and thermally annealed thin films of two indolenine and one anilino squaraines with chiral (S)-citronellyl functionalization at the nitrogen of the squaraine backbone is investigated. A pseudo polymorphic crystal structure is obtained for one of the indolenine squaraines, but thin films of both compounds are basically non-aggregated and truly isotropic as evidenced by spectroscopic ellipsometry. The anilino squaraine coalesces and readily aggregates to circular dichroic but discontinuous thin films. The extent of circular dichroism correlates with the morphology of the samples, which is quantified by Mueller matrix polarimetry in combination with atomic force microscopy. The shape of the CD spectra reinforces the hybrid Frenkel and charge-transfer excitonic nature of the characteristic double hump signatures within unpolarized absorbance spectra of previously investigated non-chiral anilino squaraines with linear alkyl chain functionalization. Such excitonic CD offers an additional design parameter for next-generation opto-electronic devices.