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Tyrosine Side-Chain Functionalities at Distinct Positions Determine the Chirooptical Properties and Supramolecular Structures of Pentameric Oligothiophenes |
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| Authors: | Dr. Marcus Bäck Dr. Robert Selegård Yogesh Todarwal Dr. Sofie Nyström Prof. Patrick Norman Dr. Mathieu Linares Prof. Per Hammarström Prof. Mikael Lindgren Prof. K. Peter R. Nilsson |
| Affiliation: | 1. Division of Chemistry, Department of Physics, Chemistry and Biology, Linköping University, 581 83 Linköpin, Sweden;2. Division of Biophysics and Bioengineering, Department of Physics, Chemistry and Biology, Linköping University, 581 83 Linköping, Sweden;3. Department of Theoretical Chemistry and Biology, KTH Royal Institute of Technology, SE-106 91 Stockholm, Sweden;4. Laboratory of Organic Electronics, ITN, Linköping University, SE-601 74 Norrköping, Sweden Scientific Visualization group, ITN, Linköping University, SE-601 74 Norrköping, Sweden Swedish e-Science Research Center (SeRC), Linköping University, 581 83 Linköping, Sweden;5. Division of Chemistry, Department of Physics, Chemistry and Biology, Linköping University, 581 83 Linköpin, Sweden Department of Physics, Norwegian University of Science and Technology, Gløshaugen, 7491 Trondheim, Norway |
| Abstract: | Control over the photophysical properties and molecular organization of π-conjugated oligothiophenes is essential to their use in organic electronics. Herein we synthesized and characterized a variety of anionic pentameric oligothiophenes with different substitution patterns of L- or D-tyrosine at distinct positions along the thiophene backbone. Spectroscopic, microscopic, and theoretical studies of L- or D-tyrosine substituted pentameric oligothiophene conjugates revealed the formation of optically active π-stacked self-assembled aggregates under acid conditions. The distinct photophysical characteristics, as well as the supramolecular structures of the assemblies, were highly influenced by the positioning of the L- or D-tyrosine moieties along the thiophene backbone. Overall, the obtained results clearly demonstrate how fundamental changes in the position of the enantiomeric side-chain functionalities greatly affect the optical properties as well as the architecture of the self-assembled supramolecular structures. |
| Keywords: | oligothiophenes chirality induced circular dichroism self-assembly chiro-optical aggregates |