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The photochemical dynamics of three classes of organic photoredox catalysts employed in organocatalyzed atom-transfer radical polymerization (O-ATRP) are studied using time-resolved optical transient absorption and fluorescence spectroscopies. The nine catalysts selected for study are examples of N-aryl and core-substituted dihydrophenazine, phenoxazine and phenothiazine compounds with varying propensities for control of polymerization outcomes. Excited singlet state lifetimes extracted from the spectroscopic measurements are reported in N,N-dimethylformamide (DMF), dichloromethane (DCM) and toluene. Ultrafast (< 200 fs to 3 ps) electronic relaxation of the photocatalysts after photoexcitation at near-UV wavelengths (318-390 nm) populates the first singlet excited state (S1). The S1-state lifetimes range from 130 ps to 40 ns with considerable dependence on the photocatalyst structure and the solvent. Competition between ground-electronic state recovery and intersystem crossing controls triplet state populations and is a minor pathway in the dihydrophenazine derivatives, but is of greater importance for phenoxazine and phenothiazine catalysts. Comparison of our results with previously reported O-ATRP performances of the various photoredox catalysis shows that high triplet-state quantum yields are not a pre-requisite for controlling polymer dispersity. For example, the 5,10-di(4-cyanophenyl)-5,10-dihydrophenazine photocatalyst, shown previously to exert good polymerization control, possesses the shortest S1-state lifetime (135 ps in DMF and 180 ps in N,N-dimethylacetamide) among the nine examples reported here, and a negligible triplet state quantum yield. The results call for a re-evaluation of the excited state properties of most significance in governing the photocatalytic behaviour of organic photoredox catalysts in O-ATRP reactions.
|Pages (from-to)||3613 - 3627|
|Number of pages||15|
|Journal||Journal of the American Chemical Society|
|Early online date||25 Feb 2021|
|Publication status||Published - 10 Mar 2021|
Bibliographical noteFunding Information:
This work was supported by EPSRC grant EP/R012695/1. The ultrafast laser laboratory at the University of Bristol was established with funding from ERC Advanced Grant CAPRI 290966. M.S. is supported by Marie Skłodowska-Curie fellowship MARCUS 793799. L.L.-B and J.T. thank the Bristol Chemical Synthesis Centre for Doctoral Training, funded by the EPSRC (EP/L015366/1), and the University of Bristol, for Ph.D. studentships. G.A. thanks the EPSRC for Ph.D. studentship funding through EP/N509619/1. T.A.A.O. acknowledges the Royal Society University Research Fellowships UF1402310 and URF\R\201007. Data are available at the University of Bristol data repository, data.bris at 10.5523/bris.jud6zf0aehpn2pjwv1klmba58 .
© 2021 American Chemical Society.
- BCS and TECS CDTs
FingerprintDive into the research topics of 'Singlet and Triplet Contributions to the Excited-State Activities of Dihydrophenazine, Phenoxazine, and Phenothiazine Organocatalysts Used in Atom Transfer Radical Polymerization'. Together they form a unique fingerprint.
8084 RS URF Renewal URF\R\201007. T Oliver
1/10/20 → 30/09/23
28/05/18 → 27/05/20
Mapping Pathways in Photocatalytic Cycles using Ultrafast Spectroscopy
1/03/18 → 28/02/21
Ultrafast photochemical dynamics of dihydrophenazine, phenoxazine and phenothiazine organic photocatalysts
Orr-Ewing, A. J. (Creator), Oliver, T. (Creator), Amoruso, G. (Creator), Sneha, M. (Creator), Lewis-Borrell, L. (Creator) & Thornton, G. L. (Creator), University of Bristol, 9 Feb 2021
DOI: 10.5523/bris.jud6zf0aehpn2pjwv1klmba58, http://data.bris.ac.uk/data/dataset/jud6zf0aehpn2pjwv1klmba58