Unusual Quartet‐Doublet Phosphorescence from the Phosphaethynyl Radical, CP

We report the first detection of phosphorescence from the phosphaethynyl radical. This rare instance of quartet‐doublet emission, studied here in solid argon, is presumably promoted by efficient intersystem crossing from the originally photoexcited doublet (B2Σ+) to the adjacent second quartet state...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2022-10, Vol.61 (43), p.e202210521-n/a
Main Authors: Ganesan, Elavenil, Custer, Thomas, Lawzer, Arun‐Libertsen, Guillemin, Jean‐Claude, Kołos, Robert
Format: Article
Language:English
Subjects:
Argon
Carbon Monophosphide
Chemical Sciences
CP Radical
Emission analysis
Phosphorescence
Progressions
Quartet-Doublet Emission
Radical Phosphorescence
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Summary:We report the first detection of phosphorescence from the phosphaethynyl radical. This rare instance of quartet‐doublet emission, studied here in solid argon, is presumably promoted by efficient intersystem crossing from the originally photoexcited doublet (B2Σ+) to the adjacent second quartet state, 14Δ. Vibronic progressions were traced for the a4Σ+‐X2Σ+ and a4Σ+‐A2Пi systems from their origins up to (v′=0)→(v′′=5) and (v′=0)→(v′′=2) bands, respectively. The measured phosphorescence lifetime is 108 ± 3 ms. CP is generated by photolysis of phosphaethyne (HCP) isolated in solid argon. Phosphorescence of the radical, observed after the B2Σ+‐X2Σ+ photoexcitation, is assisted by an intersystem crossing from B2Σ+ to the adjacent second quartet state, 14Δ. Intense, well‐resolved vibronic progressions were traced for a4Σ+‐X2Σ+ and a4Σ+‐A2Πi emission systems. Phosphorescence lifetime is on the order of 0.1 s.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202210521