Decoding Coordination Geometry Enforcement in Metallo-supramolecular Polymer Networks from Macroscopic Rheological Signatures,Macromolecules

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Decoding Coordination Geometry Enforcement in Metallo-supramolecular Polymer Networks from Macroscopic Rheological Signatures
Macromolecules ( IF 5.1 ) Pub Date : 2024-09-11 , DOI: 10.1021/acs.macromol.4c01380
Mostafa Ahmadi ₁ , Albert Poater ₂ , Sebastian Seiffert ₁

Affiliation

The control over coordination geometry in metallo-supramolecular polymer networks not only helps developing new polymer structures but also provides new measures of metal complex characteristics. Herein, we compare multiscale characteristics of networks obtained by homo- and heteroleptic association of mono-, bi-, and tridentate ligands, as reflected in rheological measurements and DFT calculations. Accordingly, tetra-arm poly(ethylene glycol) (tetraPEG), functionalized with pyridine, phenanthroline, and terpyridine, form parent homoleptic networks, while their combination with a tetraPEG functionalized by the sterically demanding dimesitylene substituted phenanthroline forms heteroleptic networks. Among all employed transition metal ions, only Cu^+/2+ and Pd²⁺ comply with the coordination geometry necessities of all parent and mixed networks, ranging from trigonal to octahedral, providing good candidates for wide network topology rearrangements. Our rheological measurements and DFT calculations demonstrate that the stability of homoleptic complexes depends primarily on metal identity, whereas that of heteroleptic equivalents increases with increasing the denticity of the slim ligand, being a complex function of steric, electronic, and π–π interactions.

中文翻译：

从宏观流变特征解码金属超分子聚合物网络中的配位几何强化

对金属超分子聚合物网络中配位几何形状的控制不仅有助于开发新的聚合物结构，而且还提供了金属配合物特性的新测量方法。在此，我们比较了通过单齿、双齿和三齿配体的同配和杂配缔合获得的网络的多尺度特征，如流变测量和 DFT 计算中所反映的。因此，用吡啶、菲咯啉和三联吡啶官能化的四臂聚乙二醇(tetraPEG)形成母体均配网络，而它们与由空间要求严格的二均三甲苯取代的菲咯啉官能化的tetraPEG组合形成杂配网络。在所有使用的过渡金属离子中，只有Cu ^+/2+和Pd ²⁺符合所有母体网络和混合网络（从三角到八面体）的配位几何要求，为广泛的网络拓扑重排提供了良好的候选者。我们的流变测量和 DFT 计算表明，均配配合物的稳定性主要取决于金属特性，而杂配当量的稳定性随着细配体密度的增加而增加，是空间、电子和 π-π 相互作用的复杂函数。

更新日期：2024-09-11

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