Multiple Pathways for the Primary Step of the Spiropyran Photochromic Reaction: A CASPT2//CASSCF Study

Liu, Fengyi; Morokuma, Keiji

doi:10.1021/ja402868b

Cited by 92 publications

(126 citation statements)

References 43 publications

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“…This is reflected in the HOOP dihedral angle of 1208 at the S 1 /S 0 conical intersection of the double mutant (see Figure 2 a). Such HOOP motion has previously been reported in the photoisomerization of the chromophores of rhodopsin [15] and photoactive yellow proteins [16] as well as in photochromic spiropyran [17] (but, to our knowledge, not yet in GFPs). We emphasize that the HOOP motion in the central CH unit does not occur in vacuo, but only in the S65T/H148D double mutant during the late stages of the photoisomerization (see Section 2.3 in the Supporting Information).…”

Section: Angewandte Chemiesupporting

confidence: 72%

Concerted Asynchronous Hula‐Twist Photoisomerization in the S65T/H148D Mutant of Green Fluorescent Protein

et al. 2014

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Fluorescence emission of wild-type green fluorescent protein (GFP) is lost in the S65T mutant, but partly recovered in the S65T/H148D double mutant. These experimental findings are rationalized by a combined quantum mechanics/molecular mechanics (QM/MM) study at the QM(CASPT2// CASSCF)/AMBER level. A barrierless excited-state proton transfer, which is exclusively driven by the Asp148 residue introduced in the double mutant, is responsible for the ultrafast formation of the anionic fluorescent state, which can be deactivated through a concerted asynchronous hula-twist photoisomerization. This causes the lower fluorescence quantum yield in S65T/H148D compared to wild-type GFP. Hydrogen out-of-plane motion plays an important role in the deactivation of the S65T/H148D fluorescent state

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Section: Angewandte Chemiesupporting

confidence: 72%

Concerted Asynchronous Hula‐Twist Photoisomerization in the S65T/H148D Mutant of Green Fluorescent Protein

et al. 2014

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“…A barrier in the excited state would lead to a rate equation similar to Equation . Results from theoretical work and time‐resolved spectroscopy indicate that after ring opening, the molecules are present in a cis‐isomerized intermediate state. Accordingly, the perpendicularly oriented MC isomer directly after photoexcitation needs to undergo an unfolding process to a planar TTC configuration.…”

Section: Resultsmentioning

confidence: 99%

Reversible Switching of Spiropyran Molecules in Direct Contact With a Bi(111) Single Crystal Surface

Nickel

Bernien

Kraffert

et al. 2017

Adv Funct Materials

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Photochromic molecular switches immobilized by direct contact with surfaces typically show only weak response to optical excitation, which often is not reversible. In contrast, here, it is shown that a complete and reversible ringopening and ring-closing reaction of submonolayers of spironaphthopyran on the Bi(111) surface is possible. The ring opening to the merocyanine isomer is initiated by ultraviolet light. Switching occurs in a two-step process, in which after optical excitation, an energy barrier needs to be overcome to convert to the merocyanine form. This leads to a strong temperature dependence of the conversion efficiency. Switching of the merocyanine isomer back to the closed form is achieved by a temperature increase. Thus, the process can be repeated in a fully reversible manner, in contrast to previously studied nitrospiropyran molecules on surfaces. This is attributed to the destabilization of the merocyanine isomer by the electron-donating nature of the naphtho group and the reduced van der Waals interaction of the Bi(111) surface. The result shows that molecules designed for switching in solutions need to be modified to function in direct contact with a surface.

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“…Indeed, such photo-induced ring-openings have now been explored theoretically in several heterocyclic systems, including furan, [117][118][119] pyrrole, 120 imidazole, 121 2-aminooxazole, 122 adenine, 123 spiropyran, 124,125 and -glucose.…”

Section: Isolated Molecule Dynamicsmentioning

confidence: 99%

Molecular Photofragmentation Dynamics in the Gas and Condensed Phases

Ashfold

Murdock

Oliver

2017

Annu. Rev. Phys. Chem.

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This is the submitted manuscript. The final published version (version of record) is available online via Annual Review of Physical Chemistry at http://www.annualreviews.org/doi/10.1146/annurev-physchem-052516-050756 . Please refer to any applicable terms of use of the publisher University of Bristol -Explore Bristol Research General rightsThis document is made available in accordance with publisher policies. Please cite only the published version using the reference above. Full terms of use are available: http://www.bristol.ac.uk/pure/about/ebr-terms 1 Molecular Photofragmentation Dynamics in the Gas and Condensed PhasesMichael N.R. Ashfold, Daniel Murdock and Thomas A.A. Oliver School of Chemistry, University of Bristol, Bristol, U.K., BS8 1TS AbstractExciting a molecule with a UV photon often leads to bond fission, but the final outcome of the bond cleavage is typically both molecule and phase dependent. The photodissociation of an isolated gasphase molecule can be viewed as closed system: energy and momentum are conserved, and the fragmentation is irreversible. The same is not true in a solution-phase photodissociation process.Solvent interactions may dissipate some of the photoexcitation energy prior to bond fission, and will dissipate any excess energy partitioned into the dissociation products. Products that have no analogue in the corresponding gas-phase study may arise by, for example, geminate recombination. Here we illustrate the extents to which dynamical insights from gas-phase studies can inform our understanding of the corresponding solution-phase photochemistry and how, in the specific case of photoinduced ring-opening reactions, solution-phase studies can in some cases reveal dynamical insights more clearly than the corresponding gas-phase study.Keywords photochemistry, photodissociation, photoinduced ring opening, non-adiabatic dynamics, conical intersections. 2 HISTORICAL CONTEXTCiamician is recognised as a pioneer of (organic) photochemistry and an early advocate for fuel production by means of artificial photo'synthesis'. 1 His studies were performed in solution and usually driven by sunlight, at a time when the concept of the photon was yet to be fully accepted.Identifying the ultimate reaction products was in itself a major achievement, and any ideas regarding reaction mechanism were rudimentary. Even the concatenation of ideas like ground and excited electronic states, radiative and non-radiative transitions, spin multiplicity, etc, into what would later be termed a Jablonski diagram 2 still lay far in the future.A potentially more fruitful path at that time for those curious about the mechanisms of photochemical reactions was to focus on very simple molecular systems -diatomic and 'diatomic-like' molecules. generally polychromatic) light sources were now available, and the development of grating spectrometers enabled the recording of electronic absorption spectra for many small gas-phase molecules. Vibrational and even rotational fine structure was resolved and interpreted in many such ...

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Multiple Pathways for the Primary Step of the Spiropyran Photochromic Reaction: A CASPT2//CASSCF Study

Cited by 92 publications

References 43 publications

Concerted Asynchronous Hula‐Twist Photoisomerization in the S65T/H148D Mutant of Green Fluorescent Protein

Concerted Asynchronous Hula‐Twist Photoisomerization in the S65T/H148D Mutant of Green Fluorescent Protein

Reversible Switching of Spiropyran Molecules in Direct Contact With a Bi(111) Single Crystal Surface

Molecular Photofragmentation Dynamics in the Gas and Condensed Phases

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