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Published on: October 31, 2019
Temperature‑, Concentration‑, and Solvent-Dependent M/P Helicity Switching of Double-Helical Monometallofoldamers
Kotaro Matsumura1, Daiki Tauchi2, Masashi Hasegawa2
1Department of Chemistry, Faculty of Science, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan.
Abstract:
Fluorescent double-helical monometallofoldamers [Ag-(1)2]-[PF6] were constructed by the mononuclear complexation of two bipyridine strands 1 featuring two L-shaped dibenzopyrrolo-[1,2-a]-[1,8]-naphthyridine units at both ends with a Ag-(I) cation. These monometallofoldamers exhibited double-helical/open conformational switching. [(R)-Ag-(1c)2]-[PF6] with chiral side chains induced a single-handed helix sense and enabled precise control of M/P helicity switching in response to a solvent. This complex also exhibited strong fluorescence and circularly polarized luminescence (CPL) inversion switching upon M/P helicity inversion. For instance, [(R)-Ag-(1c)2]-[PF6] exhibited positive CPL in CH2Cl2 (φF = 0.69, g lum = 1.9 × 10-3) and negative CPL in toluene (φF = 0.79, g lum = -2.0 × 10-3). This double helix also aggregated in polar solvents, which led to CPL inversion switching induced by temperature- and concentration-dependent aggregation.
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