Conjugated polymers based on metalla-aromatic building blocks.

Proc Natl Acad Sci U S A

State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.

Published: July 2022


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Article Abstract

Conjugated polymers usually require strategies to expand the range of wavelengths absorbed and increase solubility. Developing effective strategies to enhance both properties remains challenging. Herein, we report syntheses of conjugated polymers based on a family of metalla-aromatic building blocks via a polymerization method involving consecutive carbyne shuttling processes. The involvement of metal orbitals in aromatic systems efficiently reduces band gaps and enriches the electron transition pathways of the chromogenic repeat unit. These enable metalla-aromatic conjugated polymers to exhibit broad and strong ultraviolet-visible (UV-Vis) absorption bands. Bulky ligands on the metal suppress π-π stacking of polymer chains and thus increase solubility. These conjugated polymers show robust stability toward light, heat, water, and air. Kinetic studies using NMR experiments and UV-Vis spectroscopy, coupled with the isolation of well-defined model oligomers, revealed the polymerization mechanism.

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http://www.ncbi.nlm.nih.gov/pmc/articles/PMC9303910PMC
http://dx.doi.org/10.1073/pnas.2203701119DOI Listing

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