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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Programmed multiple complexation for the creation of helical structures from acyclic phenol-bipyridine oligomer ligands
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Programmed multiple complexation for the creation of helical structures from acyclic phenol-bipyridine oligomer ligands

机译：从无环酚-联吡啶低聚物配体产生螺旋结构的程序化多重络合

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摘要

Two new multidentate ligands, H_3L~1 and H_4L~2, possessing bipyridine-phenol 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 H_3L~1 with zinc(ii) and nickel(ii) acetate afforded [L~1Zn_2(OAc)] and [(L~1)_2Ni_4](OAc)_2, respectively. Each of the ligand moieties in these complexes formed a one-turn single helix. The zinc(ii) complex [L~1Zn_2(OAc)] underwent a helix compression-extension motion in solution. The complexation of the H_3L~1 ligand with iron(iii) chloride gave a dinuclear complex [(HL~1)_2Fe_2Cl_2] with a non-helical dimeric structure. The longer ligand H_4L~2 afforded a trinuclear complex [L~2Zn_3(OAc)_2] with a 1.5-turn single-helical structure upon complexation with zinc(ii) acetate. The reaction of the H_4L~2 ligand with cobalt(ii) acetate under aerobic conditions gave a mixed valence complex [L~2Co_3(OAc)_3(OMe)], which had two trivalent and one divalent cobalt ions. The structural features of the trinuclear complexes significantly depended on the metals; [L~2Co_3(OAc)_3(OMe)] had a helical pitch of 7.6 ?, which was almost twice that of [L~2Zn_3(OAc)_2] (4.0 ?).
机译：设计了具有联吡啶-苯酚重复单元的两个新的多齿配体H_3L〜1和H_4L〜2，以便多金属络合物可以以预编程的方式产生单螺旋结构。通过连续的钯催化的偶联反应合成了配体。 H_3L〜1与乙酸锌（ii）和镍（ii）的络合分别得到[L〜1Zn_2（OAc）]和[（L〜1）_2Ni_4]（OAc）_2。这些复合物中的每个配体部分形成一个单匝单螺旋。锌（ii）络合物[L〜1Zn_2（OAc）]在溶液中经历螺旋压缩-延伸运动。 H_3L〜1配体与氯化铁（iii）的络合得到具有非螺旋二聚体结构的双核络合物[（HL〜1）_2Fe_2Cl_2]。与乙酸锌（ii）络合后，较长的配体H_4L〜2提供了具有1.5转单螺旋结构的三核络合物[L〜2Zn_3（OAc）_2]。在有氧条件下，H_4L〜2配体与乙酸钴（ii）的反应生成了混合价态化合物[L〜2Co_3（OAc）_3（OMe）]，该化合物具有两个三价和一个二价钴离子。三核配合物的结构特征主要取决于金属。 [L〜2Co_3（OAc）_3（OMe）]的螺距为7.6？，几乎是[L〜2Zn_3（OAc）_2]（4.0？）的两倍。

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