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Glass transition analysis of model metallosupramolecular polyesters bearing pendant pyridine ligands with a controlled ligand–ligand distance

Polymer Journal volume 52, pages 505–514 (2020)Cite this article

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A Correction to this article was published on 01 June 2020

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Abstract

Supramolecular materials formed via metal-ligand coordination, so-called metallosupramolecular materials, have attracted attention due to their ability to modify a broad range of physical properties depending on the association strength at the coordination bond. Here, we demonstrate the correlation between the glass transition properties and the ligand distance by utilizing amorphous polyesters (denoted as PE-Py) with pendant pyridine ligands arranged homogeneously along the chain. The ligand distance is treated as the pyridine group equivalent molecular weight (MPy) and takes values of 900, 750, 550, and 420. The metal salt ZnCl2 forms coordination bonds with the pyridine ligands, generating a metallosupramolecular network. The fraction of coordinated pyridine is finely tuned by the mole ratio between the pyridine ligand and ZnCl2 ([Zn2+]/[Py]) while adhering to the stoichiometric rule. DSC measurements reveal that the variation in the glass transition temperature (Tg) with increasing [Zn2+]/[Py] is closely correlated with 1/MPy. Temperature-ramp rheological measurements are also performed, revealing that the apparent activation energy (Ea) of segmental motion has a quasi-linear relationship with 1/MPy. Thus, the present study demonstrates that the degree of restriction for segmental motion is very systematically strengthened as the ligand distance decreases, highlighting the importance of ligand distance in physical property control of metallosupramolecular materials.

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  • 01 June 2020

    An amendment to this paper has been published and can be accessed via a link at the top of the paper.

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Acknowledgements

The authors thank Mrs. A. Yamagishi at Anton Paar for her assistance with the rheological measurements. This work was supported by a grant from the Ogasawara Foundation for the Promotion of Science & Engineering. The SAXS measurements were conducted at BL8S3 of the Aichi Synchrotron Radiation Center, Aichi Science & Technology Foundation, Aichi, Japan (Proposal No. 201903070).

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  1. Department of Life Science and Applied Chemistry, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso-cho Showa-ku Nagoya-city Aichi, Nagoya-city, 466-8555, Japan

    Mikihiro Hayashi, Haruna Obara, Keisuke Shibata, Kanta Sugimoto & Akinori Takasu

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Supplementary Information: Glass transition analysis of model metallosupramolecular polyesters bearing pendant pyridine ligands with controlled ligand–ligand distance

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Hayashi, M., Obara, H., Shibata, K. et al. Glass transition analysis of model metallosupramolecular polyesters bearing pendant pyridine ligands with a controlled ligand–ligand distance. Polym J 52, 505–514 (2020). https://doi.org/10.1038/s41428-020-0304-2

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