Organopolymer with dual chromophores and fast charge-transfer properties for sustainable photocatalysis

Justin D. Smith, Abdelqader M. Jamhawi, Jacek B. Jasinski, Fabrice Gallou, Jin Ge, Rigoberto Advincula, Jinjun Liu and Sachin Handa ()
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Justin D. Smith: University of Louisville
Abdelqader M. Jamhawi: University of Louisville
Jacek B. Jasinski: University of Louisville
Fabrice Gallou: Novartis Pharma AG
Jin Ge: Case Western Reserve University
Rigoberto Advincula: Case Western Reserve University
Jinjun Liu: University of Louisville
Sachin Handa: University of Louisville

Nature Communications, 2019, vol. 10, issue 1, 1-16

Abstract: Abstract Photocatalytic polymers offer an alternative to prevailing organometallics and nanomaterials, and they may benefit from polymer-mediated catalytic and material enhancements. MPC-1, a polymer photoredox catalyst reported herein, exhibits enhanced catalytic activity arising from charge transfer states (CTSs) between its two chromophores. Oligomeric and polymeric MPC-1 preparations both promote efficient hydrodehalogenation of α-halocarbonyl compounds while exhibiting different solubility properties. The polymer is readily recovered by filtration. MPC-1-coated vessels enable batch and flow photocatalysis, even with opaque reaction mixtures, via “backside irradiation.” Ultrafast transient absorption spectroscopy indicates a fast charge-transfer process within 20 ps of photoexcitation. Time-resolved photoluminescence measurements reveal an approximate 10 ns lifetime for bright valence states. Ultrafast measurements suggest a long CTS lifetime. Empirical catalytic activities of small-molecule models of MPC-1 subunits support the CTS hypothesis. Density functional theory (DFT) and time-dependent DFT calculations are in good agreement with experimental spectra, spectral peak assignment, and proposed underlying energetics.

Date: 2019
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DOI: 10.1038/s41467-019-09316-5

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