Spotlight on Charge-Transfer Excitons in Crystalline Textured n‑Alkyl Anilino Squaraine Thin Films

Prototypical n-alkyl-terminated anilino squaraines for photovoltaic applications show characteristic double-hump absorption features peaking in the green and deep-red spectral range. These signatures result from the coupling of an intramolecular Frenkel exciton and an intermolecular charge-transfer exciton. Crystalline, textured thin films suitable for polarized spectromicroscopy have been obtained for compounds with n-hexyl (nHSQ) and n-octyl (nOSQ) terminal alkyl chains. The here-released triclinic crystal structure of nOSQ is similar to the known nHSQ crystal structure. Consequently, crystallites from both compounds show equal pronounced linear dichroism with two distinct polarization directions. The difference in the polarization angle between the two absorbance maxima cannot be derived by spatial considerations from the crystal structure alone but requires theoretical modeling. Using an essential state model, the observed polarization behavior was discovered to depend on the relative contributions of the intramolecular Frenkel exciton and the intermolecular charge-transfer exciton to the total transition dipole moment. For both nHSQ and nOSQ, the contribution of the charge-transfer exciton to the total transition dipole moment was found to be small compared to the intramolecular Frenkel exciton. Therefore, the net transition dipole moment is largely determined by the intramolecular component, resulting in a relatively small mutual difference between the polarization angles. Ultimately, the molecular alignment within the microtextured crystallites can be deduced, and with that, the excited-state transitions can be spotted.