Accidental degeneracy in the spiropyran radical cation: charge transfer between two orthogonal rings inducing ultra-efficient reactivity

Literature Information

Publication Date 2016-10-27
DOI 10.1039/C6CP06907J
Impact Factor 3.676
Authors

Luuk Kortekaas, Jorn D. Steen, Benjamin Lasorne, Wesley R. Browne


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Abstract

Photochromism of the spiropyran radical cation to the corresponding merocyanine form is investigated by a combination of electrochemical oxidation, UV/vis absorption spectroscopy, spectroelectrochemistry and first-principles calculations (TD-DFT, CAS-SCF and CAS-PT2). First, we demonstrate that the ring-opening of mono-spiropyrans occurs upon one-electron oxidation and that it can be driven photochemically as well as thermally, with trapping of the merocyanine by protonation. Second, in order to explain this experimentally observed spectroelectrochemical behaviour we suggest a theoretical mechanism based on the reactivity of the two lowest electronic excited-states, which promotes effective electron transfer from the indoline (nitrogen-ring) to the pyran (oxygen-ring) moieties (and vice versa) through a conical intersection seam of degeneracy. Characterisation of the minimum energy conical intersection on this crossing revealed that it presents a rare diabatic trapping topology. The excited state molecule cannot escape from crossing the intersection seam due to the presence of only one degeneracy-lifting coordinate that efficiently channels into the formation of the merocyanine photoproduct, so giving rise to a “kitchen sink” funnel-like effect. Therefore, assuming rapid relaxation after vertical excitation to a higher electronic state, photoconversion cannot be avoided in the D1 electronic state, which rationalises the remarkably efficient visible light driven excited-state reactivity observed experimentally.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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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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