Electronic and steric effects on the photo-induced C -> E ring-opening of structurally modified furylfulgides

Siewertsen R, Strübe F, Mattay J, Renth F, Temps F (2011)
Physical Chemistry Chemical Physics 13(34): 15699-15707.

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The ultrafast C -> E ring-opening reactions of four selectively modified furylfulgides have been studied by means of ultrafast broadband transient absorption spectroscopy after femtosecond laser excitation at lambda = 500 nm. A large difference in the dynamics was found in the case of benzannulation at the furyl moiety as an example for an electronic effect by extension of the conjugated pi-electron system compared to furylfulgides carrying sterically different alkyl substituents at the central cyclohexadiene (CHD) ring. The measured very similar spectro-temporal absorption maps for the furylfulgides with a methyl or isopropyl group at the CHD ring or an intramolecular alkyl bridge from the CHD to the furyl moiety showed two distinctive excited-state absorptions with slightly different decay times. The first time constant (tau(1) = 0.39-0.57 ps) was assigned to the rapid departure of the excited wavepacket from the Franck-Condon region. The slightly longer second decay time of tau(2) = 0.66-0.92 ps, depending on the compound, was attributed to the electronic deactivation and ring-opening through a conical intersection to the S(0) state. In contrast, the benzannulation at the furyl moiety was found to lead to a bi-phasic excited-state decay with tau(2) = 4.7 ps and a much slower additional contribution of tau(3) = 17.4 ps, approximate to 25 times longer compared to the normal furylfulgides. The drastic change is attributed to a trapping of excited molecules in a local potential energy minimum en route to the conical intersection.
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Siewertsen R, Strübe F, Mattay J, Renth F, Temps F. Electronic and steric effects on the photo-induced C -> E ring-opening of structurally modified furylfulgides. Physical Chemistry Chemical Physics. 2011;13(34):15699-15707.
Siewertsen, R., Strübe, F., Mattay, J., Renth, F., & Temps, F. (2011). Electronic and steric effects on the photo-induced C -> E ring-opening of structurally modified furylfulgides. Physical Chemistry Chemical Physics, 13(34), 15699-15707.
Siewertsen, R., Strübe, F., Mattay, J., Renth, F., and Temps, F. (2011). Electronic and steric effects on the photo-induced C -> E ring-opening of structurally modified furylfulgides. Physical Chemistry Chemical Physics 13, 15699-15707.
Siewertsen, R., et al., 2011. Electronic and steric effects on the photo-induced C -> E ring-opening of structurally modified furylfulgides. Physical Chemistry Chemical Physics, 13(34), p 15699-15707.
R. Siewertsen, et al., “Electronic and steric effects on the photo-induced C -> E ring-opening of structurally modified furylfulgides”, Physical Chemistry Chemical Physics, vol. 13, 2011, pp. 15699-15707.
Siewertsen, R., Strübe, F., Mattay, J., Renth, F., Temps, F.: Electronic and steric effects on the photo-induced C -> E ring-opening of structurally modified furylfulgides. Physical Chemistry Chemical Physics. 13, 15699-15707 (2011).
Siewertsen, Ron, Strübe, Frank, Mattay, Jochen, Renth, Falk, and Temps, Friedrich. “Electronic and steric effects on the photo-induced C -> E ring-opening of structurally modified furylfulgides”. Physical Chemistry Chemical Physics 13.34 (2011): 15699-15707.
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35 References

Data provided by Europe PubMed Central.


Satzger, Chem. Phys. Lett. 372(), 2003

Tomasello, Angew. Chem. 122(), 2010

Celani, J. Phys. Chem. 100(), 1996

Garavelli, J. Phys. Chem. A 101(), 1997

Hofmann, J. Chem. Phys. 112(), 2000
Cyclohexadiene ring opening observed with 13 fs resolution: coherent oscillations confirm the reaction path.
Kosma K, Trushin SA, Fuss W, Schmid WE., Phys Chem Chem Phys 11(1), 2009
PMID: 19081921

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