含氮双齿配体的金属超分子聚合物的结构和性能,Macromolecules

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含氮双齿配体的金属超分子聚合物的结构和性能
Macromolecules ( IF 5.1 ) Pub Date : 2023-09-07 , DOI: 10.1021/acs.macromol.3c00503
Franziska Marx ₁ , Malte Beccard ₁ , Alessandro Ianiro ₁ , Andrea Dodero ₁ , Laura N Neumann ₁ , Grégory Stoclet ₂ , Christoph Weder ₁ , Stephen Schrettl _{1,

3}

Affiliation

以金属-配体（ML）配合物为特征的超分子聚合物的固态特性，除了单体的一般性质外，还受到配体和金属盐的选择的显着影响。事实上，这些成分的变化可用于在很大范围内改变结构、热、机械和粘弹性特性。此外，某些ML复合物的动态性质可以使所得的金属超分子聚合物（MSP）具有刺激响应性，从而实现愈合、可逆粘附和力传导等功能。我们在这里报道了基于双齿配体 6-(1′-甲基苯并咪唑基)吡啶 (MBP) 的 MSP，它很容易获得，并与各种过渡金属离子形成三重配位络合物。因此，用两个MBP配体对聚(乙烯-共-丁烯)遥爪进行末端官能化，并将所得大分子单体与Zn ²⁺、Fe ²⁺或Ni ²⁺的三氟甲磺酸盐组装。所有三种 MSP 均微相分离，并根据金属离子和热历史，采用具有由 ML 配合物形成的晶域的层状或六边形形态。熔化转变温度远低于 200 °C，这使得（再）加工变得容易。此外，暴露于紫外线下可以轻松且完全修复缺陷。虽然三种 MSP 在橡胶状态下表现出相似的模量，但它们的延展性和拉伸强度取决于 ML 复合物的性质，这同样会影响长程有序和动态行为。

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Structure and Properties of Metallosupramolecular Polymers with a Nitrogen-Based Bidentate Ligand

The solid-state properties of supramolecular polymers that feature metal–ligand (ML) complexes are, in addition to the general nature of the monomer, significantly affected by the choice of ligand and metal salt. Indeed, the variation of these components can be used to alter the structural, thermal, mechanical, and viscoelastic properties over a wide ranges. Moreover, the dynamic nature of certain ML complexes can render the resulting metallosupramolecular polymers (MSPs) stimuli-responsive, enabling functions such as healing, reversible adhesion, and mechanotransduction. We here report MSPs based on the bidentate ligand 6-(1′-methylbenzimidazolyl) pyridine (MBP), which is easily accessible and forms threefold coordination complexes with various transition metal ions. Thus, a poly(ethylene-co-butylene) telechelic was end-functionalized with two MBP ligands and the resulting macromonomer was assembled with the triflate salts of either Zn²⁺, Fe²⁺, or Ni²⁺. All three MSPs microphase separate and adopt, depending on the metal ion and thermal history, lamellar or hexagonal morphologies with crystalline domains formed by the ML complexes. The melting transitions are well below 200 °C, and this permits facile (re)processing. Furthermore, defects can be readily and fully healed upon exposure to UV-light. While the three MSPs display similar moduli in the rubbery regime, their extensibility and tensile strength depend on the nature of the ML complex, which similarly affects the long-range order and dynamic behavior.

更新日期：2023-09-07

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