Helix Sense-Selective Supramolecular Polymerization Seeded by a One-Handed Helical Polymeric Assembly

  • Wei Zhang
    RIKEN Center for Emergent Matter Science, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan
  • Wusong Jin
    College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, 2999 North Renmin Road, Songjiang, Shanghai 201620, P. R. China
  • Takanori Fukushima
    Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan
  • Tadashi Mori
    Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamada-oka, Suita, Osaka 565-0871, Japan
  • Takuzo Aida
    RIKEN Center for Emergent Matter Science, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan

書誌事項

公開日
2015-10-21
資源種別
journal article
DOI
  • 10.1021/jacs.5b09878
公開者
American Chemical Society (ACS)

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説明

Helix sense-selective supramolecular polymerization was achieved using a one-handed helical nanotubular polymeric assembly as a seed. First, bipyridine (BPY)-appended achiral hexabenzocoronene ((BPY)HBC) was copolymerized noncovalently with chiral (BPY)HBC(S) (or (BPY)HBC(R)) at a molar ratio of 9:1, which, via the sergeants-and-soldiers effect, afforded a P-helical (or M-helical) nanotube, which was then treated with Cu(2+) to transform into structurally robust ((BPY)Cu)NT(P) (or ((BPY)Cu)NT(M)) with a Cu(2+)/BPY coordination polymer shell. Helical seeds ((BPY)Cu)NT(P) and ((BPY)Cu)NT(M) brought about the controlled assembly of fluorinated chiral FHBC(S) and FHBC(R) as well as achiral FHBC to yield one-handed helical nanotubular supramolecular block copolymers, in which the helical senses of the newly formed block segments were solely determined by those of the helical seeds employed. Noteworthy, FHBC(S) and FHBC(R) alone without the helical seeds form ill-defined agglomerates. Attempted supramolecular polymerization of a racemic mixture of FHBC(S) and FHBC(R) from ((BPY)Cu)NT(P) (or ((BPY)Cu)NT(M)) resulted in its chiral separation, affording P-helical (or M-helical) diastereomeric block segments composed of FHBC(S)and FHBC(R) with different thermodynamic properties.

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