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New insights in the photochromic spiro-dihydroindolizine/betaine-system

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Abstract

We have revisited the photochromic spiro-dihydroindolizine/betaine (DHI/B) system applying state-of-the-art density functional theory (DFT) calculations in combination with stationary and time-resolved absorption measurements. DHI/B-systems are becoming increasingly important as potential molecular machines, molecular switches, and photoswitchable electron-acceptors. The knowledge of the exact mechanisms of ring opening and closure, as well as of the geometries of DHI and betaine can provide critical information that will enable the design of better molecular machines and optical switches. The first surprising result concerns the electronic structure of the betaines, which is quite different than commonly assumed. The photochemical ring opening of DHI’s to betaines is a conrotatory 1,5 electrocyclic reaction, whereas the thermal ring-closing occurs in the disrotatory mode. According to our results, the electrocyclic back reaction of the betaines to the DHI is NOT rate determining, as previously thought, but instead the kinetics are dictated by the cis-trans-isomerization of the betaine.

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Authors and Affiliations

  1. Department of Chemistry, Kansas State University, 111 Willard Hall, Manhattan, KS, 66506-3701, USA

    Tej B. Shrestha, Megh Raj Pokhrel & Stefan H. Bossmann

  2. Department of Chemistry and Biochemistry, Auburn University, 179 Chemistry Building, Auburn, AL, 36849-5312, USA

    Junia Melin, Olga Dolgounitcheva, Viatcheslav G. Zakrzewski & Joseph Vincent Ortiz

  3. Department of Chemistry, Ohio State University, 100 W 18 Avenue, Columbus, OH, 43210-1185, USA

    Yao Liu & Claudia Turró

  4. Department of Chemistry, Tribhuvan University, Kirtipur, Kathmandu, Nepal

    Megh Raj Pokhrel

  5. Department of Organic Chemistry Faculty of Exact and Natural Sciences Tbilisi State University, No.3 Ilia Chavchavadze Ave., II TSU building, Tbilisi 0128, Georgia

    Eliso Gogritchiani

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  1. Tej B. Shrestha
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Shrestha, T.B., Melin, J., Liu, Y. et al. New insights in the photochromic spiro-dihydroindolizine/betaine-system. Photochem Photobiol Sci 7, 1449–1456 (2008). https://doi.org/10.1039/b814151g

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