Ultrafast laser spectroscopic study on photochromic cycloreversion dynamics in fulgide derivatives: one-photon and multiphoton-gated reactions

Ishibashi, Yukihide; Katayama, Tetsuro; Ota, Chikashi; Kobatake, Seiya; Irie, Masahiro; Yokoyama, Yasushi; Miyasaka, Hiroshi

doi:10.1039/b900999j

Cited by 30 publications

(33 citation statements)

References 73 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The subsequent HGSA decay with t 4 E 8.7 ps as averaged value reflects the slower cooling of the vibrationally excited C-molecules after conversion to the electronic ground state. The data agree well with previous studies of the ring-opening reaction of C-MeF in toluene and C-iPrF in n-hexane, 17,18 where the fast ESA component was not resolved due to the limited probe wavelength range, however. The quoted longer isomerisation time of C-MeF in toluene (1.2 ps) compared to the present value in n-hexane (0.65 ps) hints at a possible effect of solvation on the excited-state dynamics.…”

Section: Ring-opening Dynamics Of Mef Iprf and 7rfsupporting

confidence: 90%

“…We note that our assigned excited-state lifetimes are considerably longer than the quoted 1.2 ps value in a previous study of the ring-opening of a related benzofurylfulgide, where a slow component of E13.3 ps was observed in the same spectral range, but ascribed exclusively to vibrational cooling. 18 Considering the above arguments, however, in particular the clearly evident GSB refilling, that interpretation does not seem to hold. A reassignment of the 13.3 ps time constant to an excited-state decay component would give a consistent picture.…”

Section: Ring-opening Dynamics Of C-mebfmentioning

confidence: 93%

“…The photo-induced ring-opening reactions of C-MeF and C-iPrF have been previously investigated by femtosecond spectroscopy, 17,18 but the limited probe wavelength range (l probe > 400 nm) prevented a direct detection of the resulting E-products in those studies. A successive two-photon absorption was proposed to explain observed increased reaction yields after excitation with picosecond laser pulses compared to femtosecond pump pulses.…”

Section: Introductionmentioning

confidence: 99%

“…A successive two-photon absorption was proposed to explain observed increased reaction yields after excitation with picosecond laser pulses compared to femtosecond pump pulses. 18 The ring-opening of related indolyl fulgimides and fulgides has been intensively investigated by the Zinth group, [19][20][21][22][23][24][25] who found an ''activated'' excited-state reaction with isomerisation times of t = 2-15 ps attributed to a supposed shallow potential energy barrier and dependent on the solvent, excess energy, and chemical modification. No time-resolved experimental data have been available yet to our knowledge for compounds C-7rF and C-MeBF.…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

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

Siewertsen

Strübe

Mattay

et al. 2011

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

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 λ = 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 π-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 (τ(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 τ(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 τ(2) = 4.7 ps and a much slower additional contribution of τ(3) = 17.4 ps, ≈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.

show abstract

Section: Ring-opening Dynamics Of Mef Iprf and 7rfsupporting

confidence: 90%

Section: Ring-opening Dynamics Of C-mebfmentioning

confidence: 93%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

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

Siewertsen

Strübe

Mattay

et al. 2011

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

show abstract

“…The laser system used in this work has been described in detail previously. 20 The output of a femtosecond Ti:Sapphire laser (Tsunami, Spectra-Physics) pumped by the SHG of a cw Nd 3+ :YVO 4 laser (Millennia V, Spectra-Physics) was regeneratively amplified with a 1 kHz repetition rate (Spitfire, Spectra-Physics). The amplified pulse with an energy of 1 mJ/pulse and a 85 fs fwhm at a repetition rate of 1 kHz was divided into two pulses with the same energy (50%).…”

Section: Methodsmentioning

confidence: 99%

Coherent dynamics and ultrafast excited state relaxation of blue copper protein; plastocyanin

Nagasawa

Fujita

Katayama

et al. 2010

Phys. Chem. Chem. Phys.

Self Cite

View full text Add to dashboard Cite

Ultrafast transient absorption measurements in the femtosecond to picosecond time region were carried out for a blue copper protein, plastocyanin (Pc). To compare the dynamical profiles after photoexcitation upon the ligand-to-metal-charge-transfer (LMCT) band and the d-d transition band, the pump wavelength was set at wavelengths of 597 and 895 nm, respectively. The results were nearly identical, indicating that the transition from the LMCT to the lower ligand field (LF) states takes place in an ultrafast time regime of less than 40 fs. Subsequently, relaxation in the LF state occurs with a time constant of 90 fs and the system returns to the ground state with that of 250 fs. The longest time constant of 1.8 ps was attributed to the vibrational cooling in the ground state. Several wavepacket motions were observed, including Franck-Condon type motion at approximately 510 nm and a Herzberg-Teller type motion at 660-720 nm. Critically damped low-frequency oscillation of approximately 30 cm(-1) was also observed with both excitation wavelengths with the strongest amplitude around 600 nm. This oscillation could be due to the motion of the protein that is ballistically stimulated by ultrafast relaxation.

show abstract

Fulgides and Related Compounds

Gushiken¹,

Ubukata²

2011

Molecular Switches

View full text Add to dashboard Cite

Ultrafast laser spectroscopic study on photochromic cycloreversion dynamics in fulgide derivatives: one-photon and multiphoton-gated reactions

Cited by 30 publications

References 73 publications

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

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

Coherent dynamics and ultrafast excited state relaxation of blue copper protein; plastocyanin

Fulgides and Related Compounds

Contact Info

Product

Resources

About