Munzert Stefanie Martina, Stier Simon P, Schwarz Guntram, Weissman Haim, Rybtchinski Boris, Kurth Dirk G
Chemische Technologie der Materialsynthese, Julius-Maximilians-Universität Würzburg, Röntgenring 11, 97070, Würzburg, Germany.
Department of Organic Chemistry, Weizmann Institute of Science, Rehovot, 76100, Israel.
Chemistry. 2018 Feb 26;24(12):2898-2912. doi: 10.1002/chem.201701417. Epub 2017 Jul 6.
Several transition metal ions, like Fe , Co , Ni , and Zn complex to the ditopic ligand 1,4-bis(2,2':6',2''-terpyridin-4'-yl)benzene (L). Due to the high association constant, metal-ion induced self-assembly of Fe , Co , and Ni leads to extended, rigid-rod like metallo-supramolecular coordination polyelectrolytes (MEPEs) even in aqueous solution. Here, we present the kinetics of growth of MEPEs. The species in solutions are analyzed by light scattering, viscometry and cryogenic transmission electron microscopy (cryo-TEM). At near-stoichiometric amounts of the reactants, we obtained high molar masses, which follow the order Ni-MEPE≈Co-MEPE<Fe-MEPE. The experiments indicate that the kinetics of MEPE growth follows a reversible step-growth mechanism. The forward polymerization rate constants follow the order Co-MEPE<Fe-MEPE<Ni-MEPE and the growth of MEPEs can be accelerated by adding potassium acetate.
几种过渡金属离子，如Fe、Co、Ni和Zn，能与双齿配体1,4-双(2,2':6',2''-三联吡啶-4'-基)苯(L)形成配合物。由于缔合常数较高，即使在水溶液中，Fe、Co和Ni的金属离子诱导自组装也会形成延伸的、刚性棒状的金属超分子配位聚电解质(MEPEs)。在此，我们展示了MEPEs的生长动力学。通过光散射、粘度测定和低温透射电子显微镜(cryo-TEM)对溶液中的物种进行分析。在反应物接近化学计量比的情况下，我们获得了高摩尔质量，其顺序为Ni-MEPE≈Co-MEPE<Fe-MEPE。实验表明，MEPE生长动力学遵循可逆逐步增长机制。正向聚合速率常数的顺序为Co-MEPE<Fe-MEPE<Ni-MEPE，添加醋酸钾可加速MEPEs的生长。
