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Photosensitization Versus Photocyclization: Competitive Reactions of Phenylphenalenone in Its Role as Phytoanticipins in Plant Defense Strategies

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Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Marcel·lí Domingo,1, 43007 Tarragona, Spain
Cite this: J. Phys. Chem. A 2018, 122, 3, 811–821
Publication Date (Web):December 21, 2017
https://doi.org/10.1021/acs.jpca.7b11569
Copyright © 2017 American Chemical Society

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    Abstract

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    Phenalenone (PN) derivatives are involved in plant defense strategies, producing molecular singlet oxygen in a photosensitization process. Many experimental and theoretical studies determined that PN can performe this process with a quantum yield close to 1. However, it has been observed that the efficiency of some of its derivatives is much lower. This is the case of 9-phenylphenalenone (9-PhPN). To elucidate the factors that determine the different photochemistry of PN and its derivate 9-PhPN, we developed a complete active space self-consistent field/multi-configurational second-order perturbation theory study where several deactivation paths through the lowest excited states were explored. We found that the characteristics of the low-lying excited states are similar for both PN and 9-PhPN in the areas near the geometry of excitation. Consequently, the first processes that take place immediately after absorption are possible in both systems, including the population of the triplet state responsible for oxygen sensitization. However, 9-PhPN can also undergo cyclization by a bond formation between the carbonyl oxygen and a carbon atom of the phenyl substituent. This process competes favorably with population of triplet states and is responsible for the decrease of the quantum yield of oxygen sensitization in 9-PhPN relative to PN.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpca.7b11569.

    • MS-CASPT2 profiles of the PES of the lowest singlet energy states of 9-PhPN along the LIIC from the FC geometry to the 1ππ*/1nπ* crossings, perp-CI and rot-CI. MS-CASPT2 profiles of the PES of the lowest energy states of 9-PhPN along the LIIC from the minimum energy point of the nπ* state to the 1ππ*/1nπ* crossings, perp-CI and rot-CI. LIIC profiles of the PES of the lowest energy states from the 1ππ*/1nπ* rot-CI to the S1/So conical intersection. LIIC profiles of the PES of the lowest energy states from the minimum energy point of the S1/S0 CI to the minimum energy geometry of the cyclized product (PDF)

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    Cited By

    This article is cited by 8 publications.

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    2. Paul De Bonfils, Elise Verron, Catalina Sandoval-Altamirano, Pablo Jaque, Xavier Moreau, German Gunther, Pierrick Nun, Vincent Coeffard. Unusual Oxidative Dealkylation Strategy toward Functionalized Phenalenones as Singlet Oxygen Photosensitizers and Photophysical Studies. The Journal of Organic Chemistry 2020, 85 (16) , 10603-10616. https://doi.org/10.1021/acs.joc.0c01140
    3. Krittanun Deekamwong, Yuki Wada, Yiying Zhu, Pavel M Usov, Yu Tagami, Hiroyoshi Ohtsu, Masaki Kawano. Photoactive Hexaazaphenalene‐based Coordination Network as a Two‐Pathway Photosensitizer for Oxidation of Alkanes. ChemCatChem 2023, 15 (3) https://doi.org/10.1002/cctc.202201288
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    5. Julian Barrera, Edwin Patiño, Felipe Otálvaro. Improved synthesis of natural isomeric naphthoxanthenones. Tetrahedron Letters 2020, 61 (1) , 151359. https://doi.org/10.1016/j.tetlet.2019.151359
    6. Bianka Siewert, Hermann Stuppner. The photoactivity of natural products – An overlooked potential of phytomedicines?. Phytomedicine 2019, 60 , 152985. https://doi.org/10.1016/j.phymed.2019.152985
    7. Edward Owen Norman, James Lever, Robert Brkljača, Sylvia Urban. Distribution, biosynthesis, and biological activity of phenylphenalenone-type compounds derived from the family of plants, Haemodoraceae. Natural Product Reports 2019, 36 (5) , 753-768. https://doi.org/10.1039/C8NP00067K
    8. Nicholas S. Hill, Michelle L. Coote. A comparison of methods for theoretical photochemistry: Applications, successes and challenges. 2019, 203-285. https://doi.org/10.1016/bs.arcc.2019.08.008