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Direct Evidence of Heteroleptic Complexation in the Macroscopic Dynamics of Metallo-supramolecular Polymer Networks

Cite this: Macromolecules 2021, 54, 15, 7113–7124
Publication Date (Web):May 24, 2021
Copyright © 2021 The Authors. Published by American Chemical Society

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    Abstract Image

    Heteroleptic complexes are widely employed in small-molecule supramolecular arrays for the construction of complex architectures or for inducing nanoscopic rearrangements upon application of external stimuli that change the coordination-geometry preference. Despite this potential, they are rarely employed in the development of metallo-supramolecular polymer networks; this is unfortunate as that strategy might actually provide a tool to build highly homogeneous model-type networks that could form a basis for both a myriad of elementary investigations on transient networks and for their use in rational soft-functional materials design. To close that gap, we mix aqueous solutions of terpyridine- and phenanthroline-functionalized tetra-arm poly(ethylene glycol) (tetraPEG) precursors right at the overlap concentration and form physical hydrogels by introducing various types of divalent transition metal ions. The formation of heteroleptic complexes is comprehended by the persistence of the network percolation at intermediate network compositions, as revealed by rheological measurements. Specifically, shear stress curves and the resulting relaxation time spectra demonstrate the emergence of a third relaxation mode, on top of those associated with homoleptic complexes, which is indicative of heteroleptic complexation. Spectroscopic analyses and DFT calculations suggest the possible formation of heteroleptic complexes with all studied metal ions, whereby their fraction and lifetime are traceable using rheological measurements in the case of networks formed by Co2+ ions. Moreover, employing over-stoichiometric Co2+-to-ligand ratios eventually results in the selective formation of heteroleptic complexes. These results not only suggest new paradigms for devising smart soft materials, but they also propose new dimensions for characterizing heteroleptic complexes.

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    Cited By

    This article is cited by 15 publications.

    1. Mostafa Ahmadi. Landscape of Network Connectivity in Transient Polymer Networks with Competing Homo- and Hetero-complementary Bonds. Macromolecules 2023, 56 (13) , 4981-4990.
    2. Mostafa Ahmadi, Lucas Löser, Gerard Pareras, Albert Poater, Kay Saalwächter, Sebastian Seiffert. Connectivity Defects in Metallo-Supramolecular Polymer Networks at Different Self-Sorting Regimes. Chemistry of Materials 2023, 35 (10) , 4026-4037.
    3. Mostafa Ahmadi, Albert Poater, Sebastian Seiffert. Self-Sorting of Transient Polymer Networks by the Selective Formation of Heteroleptic Metal–Ligand Complexes. Macromolecules 2023, 56 (4) , 1390-1401.
    4. Franziska Marx, Subhajit Pal, Julien Sautaux, Nazim Pallab, Grégory Stoclet, Christoph Weder, Stephen Schrettl. Plasticization of a Semicrystalline Metallosupramolecular Polymer Network. ACS Polymers Au 2023, 3 (1) , 132-140.
    5. Mostafa Ahmadi, Ahad Hanifpour, Sina Ghiassinejad, Evelyne van Ruymbeke. Polyolefins Vitrimers: Design Principles and Applications. Chemistry of Materials 2022, 34 (23) , 10249-10271.
    6. Taka-aki Okamura, Mami Ishikawa, Kiyotaka Onitsuka. Unsymmetrical Metallosupramolecular Polycondensation of Expanded l-Amino Acid Containing Platinum(II) Complex in Nonpolar Solvents. ACS Applied Polymer Materials 2022, 4 (12) , 9472-9481.
    7. Mostafa Ahmadi, Paola Nicolella, Sebastian Seiffert. Network Percolation in Transient Polymer Networks with Temporal Hierarchy of Energy Dissipation. Macromolecules 2022, 55 (22) , 9960-9971.
    8. Mostafa Ahmadi, Farhad Panahi, Naeimeh Bahri-Laleh, Mohammad Sabzi, Gerard Pareras, Bruno N. Falcone, Albert Poater. pH-Responsive Gelation in Metallo-Supramolecular Polymers Based on the Protic Pyridinedicarboxamide Ligand. Chemistry of Materials 2022, 34 (13) , 6155-6169.
    9. Thanh Nhan Nguyen, Ngoc Minh Tran, In-Hyeok Park, Hyojong Yoo. Heteroleptic Triple-Stranded Metallosupramolecules with Hydrophobic Inner Voids. ACS Omega 2022, 7 (15) , 13067-13074.
    10. Arezoo Dashti, Mostafa Ahmadi, Vahid Haddadi-Asl, Saeid Ahmadjo, Seyed Mohammad Mahdi Mortazavi. Tandem Coordinative Chain Transfer Polymerization for Long Chain Branched Polyethylene: The Role of Chain Displacement. European Polymer Journal 2023, 10 , 112008.
    11. Jiafu Shen, Yu Dai, Fan Xia, Xiaojin Zhang. Role of divalent metal ions in the function and application of hydrogels. Progress in Polymer Science 2022, 135 , 101622.
    12. Batoul Hosseinzadeh, Mostafa Ahmadi. Coordination geometry in metallo-supramolecular polymer networks. Coordination Chemistry Reviews 2022, 471 , 214733.
    13. Hao Chen, Kun Tong. The Contributions of Supramolecular Kinetics to Dynamics of Supramolecular Polymers. ChemPlusChem 2022, 87 (10)
    14. Amir Jangizehi, Mostafa Ahmadi, Sarah Pschierer, Paola Nicolella, Hailong Li, Katrin Amann-Winkel, Sebastian Seiffert. Metal–ligand complexation and clustering in mussel-inspired side-chain functionalized supramolecular hydrogels. Soft Matter 2022, 18 (36) , 6836-6847.
    15. Batoul Hosseinzadeh, Mostafa Ahmadi. Coordination Geometry in Metallo-Supramolecular Polymer Networks. SSRN Electronic Journal 2022, 357

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