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Chiroptical rhythmicity, Part 1: Description of a novel phenomenon
1Department of Chemistry, Georgetown University, Washington, DC 20057, USA.
Abstract:
A novel chiroptical phenomenon named "chiroptical rhythmicity" is described. Chiroptical rhythmicity consists of multiple reversible circular dichroism Cotton effect sign inversions that follow a rhythmical pattern with respect to the continuous addition of a ligand (L-His) to the sample (a septi(p-phenylene)-based receptor bound to phosphatidylcholine bilayers). Decrease and blue-shift of the 1La absorption of the oligophenylene chromophore indicated that partial "H" aggregation occurs during chiroptical rhythmicity. Based on stereochemical considerations for monomeric and tetrameric oligophenylenes, a hypothetical mechanism is discussed.
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