Ladder-type pentaphenyl chromophores have a rigid, planar π-system and show bright fluorescence featuring pronounced vibrational structure. Such moieties are ideal for studying interchromophoric interactions and delocalization of electronic excitations. We report the synthesis of helical polymers with a rigid square structure based on spiro-linked ladder-type pentaphenyl units. The variation of circular dichroism with increasing chain length provides direct evidence for delocalization of electronic excitations over at least 10 monomeric units. The change in the degree of circular polarization of the fluorescence across the vibronic side bands shows that vibrational motion can localize the excitation dynamically to almost one single unit through breakdown of the Born-Oppenheimer approximation. The dynamic conversion between delocalized and localized excited states provides a new paradigm for interpreting circular dichroism in helical polymers such as proteins and polynucleic acids.
Download full-text PDF |
Source |
---|---|
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC10107742 | PMC |
http://dx.doi.org/10.1002/anie.202211946 | DOI Listing |
Angew Chem Int Ed Engl
January 2023
Department of Chemistry, Macromolecular Chemistry group (BUWmakro), and Wuppertal Institute for Smart Materials and Systems (CM@S), Bergische Universität Wuppertal, Gauss-Str. 20, 42119, Wuppertal, Germany.
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!