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Issue 45, 2013
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Programmed multiple complexation for the creation of helical structures from acyclic phenolbipyridine oligomer ligands

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Abstract

Two new multidentate ligands, H3L1 and H4L2, possessing bipyridinephenol repetitive units were designed so that the multi-metal complexation could produce a single-helical structure in a pre-programmed fashion. The ligands were synthesized by successive palladium-catalyzed coupling reactions. The complexation of H3L1 with zinc(II) and nickel(II) acetate afforded [L1Zn2(OAc)] and [(L1)2Ni4](OAc)2, respectively. Each of the ligand moieties in these complexes formed a one-turn single helix. The zinc(II) complex [L1Zn2(OAc)] underwent a helix compression–extension motion in solution. The complexation of the H3L1 ligand with iron(III) chloride gave a dinuclear complex [(HL1)2Fe2Cl2] with a non-helical dimeric structure. The longer ligand H4L2 afforded a trinuclear complex [L2Zn3(OAc)2] with a 1.5-turn single-helical structure upon complexation with zinc(II) acetate. The reaction of the H4L2 ligand with cobalt(II) acetate under aerobic conditions gave a mixed valence complex [L2Co3(OAc)3(OMe)], which had two trivalent and one divalent cobalt ions. The structural features of the trinuclear complexes significantly depended on the metals; [L2Co3(OAc)3(OMe)] had a helical pitch of 7.6 Å, which was almost twice that of [L2Zn3(OAc)2] (4.0 Å).

Graphical abstract: Programmed multiple complexation for the creation of helical structures from acyclic phenol–bipyridine oligomer ligands

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Publication details

The article was received on 11 May 2013, accepted on 21 Jun 2013, published on 22 Jul 2013 and first published online on 22 Jul 2013


Article type: Paper
DOI: 10.1039/C3DT51240A
Citation: Dalton Trans., 2013,42, 15974-15986
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    Programmed multiple complexation for the creation of helical structures from acyclic phenolbipyridine oligomer ligands

    S. Akine, H. Nagumo and T. Nabeshima, Dalton Trans., 2013, 42, 15974
    DOI: 10.1039/C3DT51240A

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