Journal article
Structure-Dependent Electron Transfer Rates for Dihydrophenazine, Phenoxazine, and Phenothiazine Photoredox Catalysts Employed in Atom Transfer Radical Polymerization
The journal of physical chemistry. B, Vol.125(28), pp.7840-7854
07/22/2021
DOI: 10.1021/acs.jpcb.1c05069
PMID: 34237215
Abstract
Organic photocatalysts (PCs) are gaining popularity in applications of photoredox catalysis, but few studies have explored their modus operandi. We report a detailed mechanistic investigation of the electron transfer activation step of organocatalyzed atom transfer radical polymerization (O-ATRP) involving electronically excited organic PCs and a radical initiator, methyl 2-bromopropionate (MBP). This study compares nine N-aryl modified PCs possessing dihydrophenazine, phenoxazine, or phenothiazine core chromophores. Transient electronic and vibrational absorption spectroscopies over subpicosecond to nanosecond and microsecond time intervals, respectively, track spectroscopic signatures of both the reactants and products of photoinduced electron transfer in N,N-dimethylformamide, dichloromethane, and toluene solutions. The rate coefficients for electron transfer exhibit a range of values up to ∼1010 M–1 s–1 influenced systematically by the PC structures. These rate coefficients are an order of magnitude smaller for catalysts with charge transfer character in their first excited singlet (S1) or triplet (T1) states than for photocatalysts with locally excited character. The latter species show nearly diffusion-limited rate coefficients for the electron transfer to MBP. The derived kinetic parameters are used to model the contributions to electron transfer from the S1 state of each PC for different concentrations of MBP. Comparisons of singlet and triplet reactivity for one of the phenoxazine PCs reveal that the rate coefficient k ET(T1) = (2.7 ± 0.3) × 107 M–1 s–1 for electron transfer from the T1 state is 2 orders of magnitude lower than that from the S1 state, k ET(S1) = (2.6 ± 0.4) × 109 M–1 s–1. The trends in bimolecular electron transfer rate coefficients are accounted for using a modified Marcus theory for dissociative electron transfer.
Details
- Title: Subtitle
- Structure-Dependent Electron Transfer Rates for Dihydrophenazine, Phenoxazine, and Phenothiazine Photoredox Catalysts Employed in Atom Transfer Radical Polymerization
- Creators
- Mahima Sneha - School of ChemistryAditi Bhattacherjee - School of ChemistryLuke Lewis-Borrell - School of ChemistryIan P Clark - Central Laser Facility, Research Complex at Harwell, Science and Technology Facilities Council, Rutherford Appleton LaboratoryAndrew J Orr-Ewing - School of Chemistry
- Resource Type
- Journal article
- Publication Details
- The journal of physical chemistry. B, Vol.125(28), pp.7840-7854
- DOI
- 10.1021/acs.jpcb.1c05069
- PMID
- 34237215
- NLM abbreviation
- J Phys Chem B
- ISSN
- 1520-6106
- eISSN
- 1520-5207
- Publisher
- American Chemical Society
- Grant note
- DOI: 10.13039/501100000266, name: Engineering and Physical Sciences Research Council, award: EP/R012695/1; DOI: 10.13039/100010665, name: H2020 Marie SkÅ?odowska-Curie Actions, award: 793799; DOI: 10.13039/100011199, name: FP7 Ideas: European Research Council, award: 290966; DOI: 10.13039/501100000883, name: University of Bristol
- Language
- English
- Date published
- 07/22/2021
- Academic Unit
- Chemistry
- Record Identifier
- 9984216599402771
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