Benzothiadiazole-based linear conjugated polymers bearing Re(I) complexes for CO2 photoreduction
Journal
Journal of CO2 Utilization
Journal Volume
110
Start Page
103515
ISSN
22129820
Date Issued
2026-08
Author(s)
Yu, Yu-Chen
Yeh, Yu-Chieh
Chang, Ching-Hsiang
Chen, Yen-Chih
Lee, Min-Kai
Chen, Tsung-Yi
Pao, Chih-Wen
Li, Yun-Ming
Abstract
Linear conjugated polymers represent an underexplored architecture for CO2 photoreduction compared with cross-linked polymers and covalent organic frameworks. Here, two polymers incorporating benzothiadiazole and bipyridine units have been synthesized and coordinated with Re(CO)3Cl. Structural characterization has confirmed successful polymer formation and Re chelation. The resulting polymers exhibit favorable optical and electrochemical properties and achieve turnover numbers for CO (TONCO) of 60.7 and 52.1 within 6 h, significantly outperforming the molecular reference chlorotricarbonyl(2,2′-bipyridine)rhenium(I) (TONCO = 14.4). Control experiments and 13CO2 isotope labeling have verified that the produced CO originates from CO2. Repetitive catalytic runs have further revealed enhanced stability of the polymer catalysts relative to the molecular complex. Transient absorption spectroscopy shows that longer excited-state absorption lifetimes correlate with higher photocatalytic activity, while time-dependent DFT calculations provide insight into the underlying electronic transitions. These results demonstrate that linear conjugated polymers coordinated with Re complexes are efficient and stable photocatalysts, highlighting the critical role of conjugated moiety selection and molecular design in optimizing CO2 photoreduction performance.
Subjects
CO
CO2 photoreduction
Conjugated polymer
DFT calculation
Rhenium
Transient absorption spectroscopy
Publisher
Elsevier Ltd
Type
journal article