Deactivation of the first excited singlet state of thiophenols

Literature Information

Publication Date 2006-02-23
DOI 10.1039/B516924K
Impact Factor 3.676
Authors

Yasser M. Riyad, Sergej Naumov, Ralf Hermann, Ortwin Brede


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Abstract

On the bases of picosecond and nanosecond laser flash photolysis with detection by emission and absorption spectroscopy, a quantitative description is given of all deactivation channels of the first excited singlet state of thiophenols ArSH(S1) such as fluorescence, intersystem crossing (ISC), chemical dissociation into radicals, and radiation-less internal conversion (IC). For this purpose, the photolysis of thiophenol and its methyl-, methoxy-, and chloro-substituted derivatives was studied in solvents of increasing polarity: 1-chlorobutane, ethanol, and acetonitrile. The fluorescence lifetime of the thiophenols was found to range from some hundreds of picoseconds up to a few nanoseconds, correlating with fluorescence quantum yields between 0.001–0.040, at room temperature. Depending on the substitution pattern of the aromatic ring, the quantum yield of the S–H bond dissociation was found to be between 0.3–0.5, irrespective of the solvent polarity. In laser photolysis, no triplet formation of the investigated compounds could be observed neither by the direct way nor by subsequent sensitization with β-carotene. As a difference to the total, the radiation-less internal conversion (ΦIC ≥ 0.5) was found to be the dominating process.

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Contents

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DOI: 10.1039/B922411B

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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