Redefining the established understanding of excitation dynamics of photochromic oxazines

Literature Information

Publication Date 2015-06-04
DOI 10.1039/C5CP02143J
Impact Factor 3.676
Authors

V. Voiciuk, K. Redeckas, V. Martynaitis, R. Steponavičiūtė, A. Šačkus, M. Vengris


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Abstract

Since the introduction of photochromic indolo-benzoxazines, difference absorption of these photoexcited compounds has been assigned to the ground state of the ring-opened isomer. This assignment relies on the alleged resemblance of the spectra of photo- and chemically induced forms. In this paper, we expose the issue of the discrepancy between the absorption spectra of photoproducts and the corresponding chemically opened forms. As a result, a substantial change in the current explanation of photodynamics of photochromic oxazines is proposed. The spectral features earlier ascribed to the photoproduct are suggested to arise due to the absorption of the triplet state. This hypothesis was tested and confirmed in acetonitrile by measuring the effect of oxygen quenching of photoproduct states. In view of this interpretation, light-induced ring opening does not occur in indolo-benzoxazines dissolved in acetonitrile, and, consequently these molecules should no longer be regarded as molecular switches. On the other hand, we show that methanol solution under UV light does produce small amounts of ring-opened form of the molecule.

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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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