The Kinetics of Growth of Metallo-supramolecular Polyelectrolytes in Solution.
The Kinetics of Growth of Metallo-supramolecular Polyelectrolytes in Solution.
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DOI：
10.1002/chem.201701417
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发表时间：
2018-02
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通讯作者：
Stefanie Martina Munzert;S. Stier;G. Schwarz;H. Weissman;B. Rybtchinski;D. Kurth
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作者：
Stefanie Martina Munzert;S. Stier;G. Schwarz;H. Weissman;B. Rybtchinski;D. Kurth
几种过渡金属离子如Fe 2+、Co 2+、Ni 2+和Zn 2+与双配位配体1，4-双（2，2 '：6'，2“-三联吡啶-4 '-基）苯（L）络合。由于高的缔合常数，金属离子诱导的Fe 2+，Co 2+，Ni 2+的自组装导致扩展的，刚性棒状的金属-超分子配位聚电解质（MEPE），即使在水溶液中。在这里，我们提出了MEPE的增长动力学。通过光散射、粘度计和低温透射电子显微镜（cryo-TEM）分析溶液中的物种。在接近化学计量的反应物量下，我们获得了高摩尔质量，其遵循顺序Ni-MEPE> Co-MEPE<Fe-MEPE。实验表明，MEPE生长动力学遵循可逆的逐步生长机制。正向聚合速率常数的顺序为Co-MEPE<Fe-MEPE<Ni-MEPE，乙酸钾的加入可促进MEPE的生长。
Several transition metal ions, like Fe2+ , Co2+ , Ni2+ , and Zn2+ 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 Fe2+ , Co2+ , and Ni2+ 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.