Tuning of switching properties and excited-state dynamics of fulgides by structural modifications

Siewertsen R, Strübe F, Mattay J, Renth F, Temps F (2011)
Physical Chemistry Chemical Physics 13(9): 3800-3808.

Journal Article | Published | English

No fulltext has been uploaded

Author
; ; ; ;
Abstract
The ultrafast photo-induced dynamics of the E-isomers of four selected photochromic fulgides with distinct structural motifs have been elucidated by femtosecond broadband transient absorption spectroscopy in n-hexane as solvent. E -> C and E -> Z isomerisations, respectively, with time constants of similar to 0.12 +/- 0.02 ps and similar to 0.34 +/- 0.03 ps taking place in parallel were found for derivatives with a methyl substituent at the central hexatriene (HT) unit. In contrast, fulgides with increased steric constraints by an iso-propyl substituent or by intramolecular bridging displayed virtually zero E -> Z isomerisation, but instead a desired accelerated and more efficient ring closure in a reaction time of only similar to 50 +/- 10 fs. Both photoisomerisations appear to follow excited-state pathways with distinctive conical intersections. For the ring closure, direct barrierless pathways with steep downhill gradients are likely. Furthermore, the results indicate conformer-specific reactions, with ring closure exclusively by the E-alpha conformer and E -> Z isomerisation predominantly by the E-beta conformer, because the E-alpha -> Z channel is unfavoured by the faster and kinetically more competitive E-alpha -> C reaction. DFT calculations of the equilibrium structures showed that the sterically demanding groups at the HT unit shift the conformer equilibria towards the E-alpha conformers. At the same time, they appear to cause a favourable pre-orientation of the furyl unit that accelerates the conrotatory ring closure in the E-alpha -> C reaction. Benzo-annulation of the furyl unit has little effect on the observed dynamics. Overall, the results demonstrate how the excited-state dynamics and thereby the photoswitching properties of fulgides can be successfully tuned and improved by structural modifications at the chromophores.
Publishing Year
ISSN
eISSN
PUB-ID

Cite this

Siewertsen R, Strübe F, Mattay J, Renth F, Temps F. Tuning of switching properties and excited-state dynamics of fulgides by structural modifications. Physical Chemistry Chemical Physics. 2011;13(9):3800-3808.
Siewertsen, R., Strübe, F., Mattay, J., Renth, F., & Temps, F. (2011). Tuning of switching properties and excited-state dynamics of fulgides by structural modifications. Physical Chemistry Chemical Physics, 13(9), 3800-3808.
Siewertsen, R., Strübe, F., Mattay, J., Renth, F., and Temps, F. (2011). Tuning of switching properties and excited-state dynamics of fulgides by structural modifications. Physical Chemistry Chemical Physics 13, 3800-3808.
Siewertsen, R., et al., 2011. Tuning of switching properties and excited-state dynamics of fulgides by structural modifications. Physical Chemistry Chemical Physics, 13(9), p 3800-3808.
R. Siewertsen, et al., “Tuning of switching properties and excited-state dynamics of fulgides by structural modifications”, Physical Chemistry Chemical Physics, vol. 13, 2011, pp. 3800-3808.
Siewertsen, R., Strübe, F., Mattay, J., Renth, F., Temps, F.: Tuning of switching properties and excited-state dynamics of fulgides by structural modifications. Physical Chemistry Chemical Physics. 13, 3800-3808 (2011).
Siewertsen, Ron, Strübe, Frank, Mattay, Jochen, Renth, Falk, and Temps, Friedrich. “Tuning of switching properties and excited-state dynamics of fulgides by structural modifications”. Physical Chemistry Chemical Physics 13.9 (2011): 3800-3808.
This data publication is cited in the following publications:
This publication cites the following data publications:

5 Citations in Europe PMC

Data provided by Europe PubMed Central.

Ultrafast Z → E photoisomerisation of structurally modified furylfulgides.
Renth F, Siewertsen R, Strube F, Mattay J, Temps F., Phys Chem Chem Phys 16(36), 2014
PMID: 25105666
Ultrafast polyene dynamics: the ring opening of 1,3-cyclohexadiene derivatives.
Arruda BC, Sension RJ., Phys Chem Chem Phys 16(10), 2014
PMID: 24457943
Photochemical dynamics of E-iPr-furylfulgide.
Schonborn JB, Koslowski A, Thiel W, Hartke B., Phys Chem Chem Phys 14(35), 2012
PMID: 22850439
Electronic and steric effects on the photo-induced C→E ring-opening of structurally modified furylfulgides.
Siewertsen R, Strube F, Mattay J, Renth F, Temps F., Phys Chem Chem Phys 13(34), 2011
PMID: 21799957

60 References

Data provided by Europe PubMed Central.

Wavelength and solvent independent photochemistry: the electrocyclic ring-closure of indolylfulgides.
Cordes T, Herzog TT, Malkmus S, Draxler S, Brust T, Digirolamo JA, Lees WJ, Braun M., Photochem. Photobiol. Sci. 8(4), 2009
PMID: 19337667
Fluorescent Switches Based on Photochromic Compounds
Cusido, European Journal of Organic Chemistry 2009(13), 2009
Ring-opening reaction of a trifluorinated indolylfulgide: mode-specific photochemistry after pre-excitation.
Draxler S, Brust T, Malkmus S, DiGirolamo JA, Lees WJ, Zinth W, Braun M., Phys Chem Chem Phys 11(25), 2009
PMID: 19562131
Ultrafast laser spectroscopic study on photochromic cycloreversion dynamics in fulgide derivatives: one-photon and multiphoton-gated reactions
Ishibashi, New Journal of Chemistry 33(6), 2009
Photochemistry with thermal versus optical excess energy: Ultrafast cycloreversion of indolylfulgides and indolylfulgimides
Brust, Journal of Photochemistry and Photobiology A Chemistry 207(2-3), 2009
Highly efficient reversible Z-E photoisomerization of a bridged azobenzene with visible light through resolved S(1)(n pi*) absorption bands.
Siewertsen R, Neumann H, Buchheim-Stehn B, Herges R, Nather C, Renth F, Temps F., J. Am. Chem. Soc. 131(43), 2009
PMID: 19827776
Two-photon three-dimensional optical storage memory.
Dvornikov AS, Walker EP, Rentzepis PM., J Phys Chem A 113(49), 2009
PMID: 19856937
Coherent ultrafast torsional motion and isomerization of a biomimetic dipolar photoswitch.
Briand J, Bram O, Rehault J, Leonard J, Cannizzo A, Chergui M, Zanirato V, Olivucci M, Helbing J, Haacke S., Phys Chem Chem Phys 12(13), 2010
PMID: 20237707

Export

0 Marked Publications

Open Data PUB

Web of Science

View record in Web of Science®

Sources

PMID: 21210030
PubMed | Europe PMC

Search this title in

Google Scholar