Handa, Sachin and Gallou, Fabrice (2019) Organopolymer with dual chromophores and fast charge-transfer properties for sustainable photocatalysis. Nature Communications, 10 (1). pp. 1837-1841. ISSN 20411723

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.

Item Type:	Article
Date Deposited:	11 Jun 2019 00:45
Last Modified:	11 Jun 2019 00:45
URI:	https://oak.novartis.com/id/eprint/37012