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Issue 1, 2015
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Chiral tether-mediated stabilization and helix-sense control of complementary metallo-double helices

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Abstract

A series of novel PtII-linked double helices were prepared by inter- or intrastrand ligand-exchange reactions of the complementary duplexes composed of chiral or achiral amidine dimer and achiral carboxylic acid dimer strands joined by trans-PtII–acetylide complexes with PPh3 ligands using chiral and achiral chelating diphosphines. The structure and stability of the PtII-linked double helices were highly dependent on the diphosphine structures. An interstrand ligand exchange took place with chiral and achiral 1,3-diphosphine-based ligands, resulting in trans-PtII-bridged double helices, whose helical structures were quite stable even in dimethyl sulfoxide (DMSO) due to the interstrand cross-link, whereas a 1,2-diphosphine-based ligand produced non-cross-linked cis-PtII-linked duplexes, resulting from an intrastrand ligand-exchange that readily dissociated into single strands in DMSO. When enantiopure 1,3-diphosphine-based ligands were used, the resulting trans-PtII-bridged double helices adopted a preferred-handed helical sense biased by the chirality of the bridged diphosphines. Interestingly, the interstrand ligand exchange with racemic 1,3-diphosphine toward an optically-active PtII-linked duplex, composed of chiral amidine and achiral carboxylic acid strands, was found to proceed in a diastereoselective manner, thus forming complete homochiral trans-PtII-bridged double helices via a unique chiral self-sorting.

Graphical abstract: Chiral tether-mediated stabilization and helix-sense control of complementary metallo-double helices

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Publication details

The article was received on 30 Jul 2014, accepted on 10 Sep 2014 and first published on 10 Sep 2014


Article type: Edge Article
DOI: 10.1039/C4SC02275K
Citation: Chem. Sci., 2015,6, 714-723
  • Open access: Creative Commons BY-NC license
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    Chiral tether-mediated stabilization and helix-sense control of complementary metallo-double helices

    M. Horie, N. Ousaka, D. Taura and E. Yashima, Chem. Sci., 2015, 6, 714
    DOI: 10.1039/C4SC02275K

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