Chiroptical response inversion upon sample flipping in thin films of a chiral benzo[1, 2-b:4, 5-b′]dithiophene-based oligothiophene. (29th June 2017)

• Record Type: Journal Article
• Authors: Albano, Gianluigi; Lissia, Margherita; Pescitelli, Gennaro; Aronica, Laura Antonella; Di Bari, Lorenzo
• Is Part Of: Materials chemistry frontiers. Volume 1:Number 10(2017)
• Page Start: 2047
• Page End: 2056
• Publication Date: 2017-06-29
• Subjects: Materials science -- Periodicals; Chemistry -- Periodicals; 540
• DOI: 10.1039/c7qm00233e
• Languages: English
• ISSNs: 2052-1529

Abstract

Abstract : Our drop-casted films display linear dichroism-linear birefringence interference (LDLB effect) with strong CD signals, which are inverted upon sample flipping. Abstract : A new chiral benzo[1, 2- b :4, 5- b ′]dithiophene-based oligothiophene has been synthesized and spectroscopically characterized in solution and in the solid state. The electronic circular dichroism (ECD) spectra of the thin films revealed the occurrence of an uncommon phenomenon, consisting of the inversion of the circular dichroism sign by sample flipping. To the best of our knowledge, this is unprecedented in samples where no preferential orientation of the chromophores has been induced, and must be due to spontaneous local anisotropies. It reveals peculiar features upon the usual solvent annealing procedure, but finally results in stable and very strong signals, which are perfectly reproduced in sign, and relative and even absolute magnitude. Although the recorded signal cannot be considered as a true ECD spectrum, it corresponds to a very large discrimination of light circular polarization, which is well explained by means of the Mueller matrix analysis and does not depend on instrumental defects. It is a genuine property of this material, which correlates with polarized optical microscopy (POM) images and only depends on the self-assembling properties of this molecule. This phenomenon may have relevant implications, on account of its strength and of the interest of oligothiophenes in current optoelectronic devices.