4.8 Article

Tuning the Charge Transport Property and Photocatalytic Activity of Anthracene-Based 1D π-d Conjugated Coordination Polymers by Interlayer Stacking

Journal

ACS APPLIED MATERIALS & INTERFACES
Volume 14, Issue 37, Pages 42171-42177

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acsami.2c13316

Keywords

1D polymer; anthracene ligands; steric effect; ultrafast spectroscopy; photocatalysis

Funding

  1. U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-AC02-06CH11357]

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This study reports three novel one-dimensional π-d-conjugated coordination polymers (CCPs) and investigates the correlation between their structural parameters and photophysical and photocatalytic properties. The results demonstrate that altering the stacking of the polymer chains through structural modification impacts their crystallinity, charge separation, and charge transport property, ultimately affecting their photocatalytic performance for hydrogen evolution reaction.
One-dimensional (1D) pi-d-conjugated coordination polymers (CCPs) with charge delocalization have attracted significant attention due to their potential application in energy conversion and storage. However, the fundamental understanding of the correlation of their structural parameters with photophysical and photocatalytic properties remains underexplored. Herein, we report three novel Cu-node anthracene-based 1D pi-d CCPs with systematic variation of steric groups (Ph > Me > H) at the 9 and 10 position of anthracene (denoted as An(Ph), An(Me), and An(H)), which is aimed at altering the stacking of the polymer chains and its impact on the inter-chain charge transport property. Using the combination of steady-state X-ray absorption spectroscopy, optical transient absorption spectroscopy, X-ray transient absorption spectroscopy, and electrochemical impedance spectroscopy, we show that the linear ligands (An(Ph), An(Me), and An(H)) with different degrees of steric groups (Ph > Me > H) introduced at the 9 and 10 position of anthracene can alter the stacking of the polymer chains and thus impact their crystallinity, charge separation, and charge transport property, which in turn impacts their photocatalytic performance for hydrogen evolution reaction.

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