Jump to main content
Jump to site search

Issue 12, 2008
Previous Article Next Article

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

Author affiliations

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.

Graphical abstract: New insights in the photochromic spiro-dihydroindolizine/betaine-system

Back to tab navigation
Please wait while Download options loads

Supplementary files

Publication details

The article was received on 14 Aug 2008, accepted on 25 Sep 2008 and first published on 23 Oct 2008


Article type: Paper
DOI: 10.1039/B814151G
Citation: Photochem. Photobiol. Sci., 2008,7, 1449-1456
  •   Request permissions

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

    T. B. Shrestha, J. Melin, Y. Liu, O. Dolgounitcheva, V. G. Zakrzewski, M. R. Pokhrel, E. Gogritchiani, J. V. Ortiz, C. Turró and S. H. Bossmann, Photochem. Photobiol. Sci., 2008, 7, 1449
    DOI: 10.1039/B814151G

Search articles by author