Pseudo-bimolecular [2+2] cycloaddition studied by time-resolved photoelectron spectroscopy
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Pseudo-bimolecular [2+2] cycloaddition studied by time-resolved photoelectron spectroscopy. / Brogaard, Rasmus Y; Boguslavskiy, Andrey E; Schalk, Oliver; Enright, Gary D; Hopf, Henning; Raev, Vitaly A; Jones, Peter G; Thomsen, Ditte L; Sølling, Theis I; Stolow, Albert.
I: Chemistry: A European Journal, Bind 17, Nr. 14, 28.03.2011, s. 3922-31.Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
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TY - JOUR
T1 - Pseudo-bimolecular [2+2] cycloaddition studied by time-resolved photoelectron spectroscopy
AU - Brogaard, Rasmus Y
AU - Boguslavskiy, Andrey E
AU - Schalk, Oliver
AU - Enright, Gary D
AU - Hopf, Henning
AU - Raev, Vitaly A
AU - Jones, Peter G
AU - Thomsen, Ditte L
AU - Sølling, Theis I
AU - Stolow, Albert
N1 - Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
PY - 2011/3/28
Y1 - 2011/3/28
N2 - The first study of pseudo-bimolecular cycloaddition reaction dynamics in the gas phase is presented. We used femtosecond time-resolved photoelectron spectroscopy (TRPES) to study the [2+2] photocycloaddition in the model system pseudo-gem-divinyl[2.2]paracyclophane. From X-ray crystal diffraction measurements we found that the ground-state molecule can exist in two conformers; a reactive one in which the vinyl groups are immediately situated for [2+2] cycloaddition and a nonreactive conformer in which they point in opposite directions. From the measured S(1) lifetimes we assigned a clear relation between the conformation and the excited-state reactivity; the reactive conformer has a lifetime of 13 ps, populating the ground state through a conical intersection leading to [2+2] cycloaddition, whereas the nonreactive conformer has a lifetime of 400 ps. Ab initio calculations were performed to locate the relevant conical intersection (CI) and calculate an excited-state [2+2] cycloaddition reaction path. The interpretation of the results is supported by experimental results on the similar but nonreactive pseudo-para-divinyl[2.2]paracyclophane, which has a lifetime of more than 500 ps in the S(1) state.
AB - The first study of pseudo-bimolecular cycloaddition reaction dynamics in the gas phase is presented. We used femtosecond time-resolved photoelectron spectroscopy (TRPES) to study the [2+2] photocycloaddition in the model system pseudo-gem-divinyl[2.2]paracyclophane. From X-ray crystal diffraction measurements we found that the ground-state molecule can exist in two conformers; a reactive one in which the vinyl groups are immediately situated for [2+2] cycloaddition and a nonreactive conformer in which they point in opposite directions. From the measured S(1) lifetimes we assigned a clear relation between the conformation and the excited-state reactivity; the reactive conformer has a lifetime of 13 ps, populating the ground state through a conical intersection leading to [2+2] cycloaddition, whereas the nonreactive conformer has a lifetime of 400 ps. Ab initio calculations were performed to locate the relevant conical intersection (CI) and calculate an excited-state [2+2] cycloaddition reaction path. The interpretation of the results is supported by experimental results on the similar but nonreactive pseudo-para-divinyl[2.2]paracyclophane, which has a lifetime of more than 500 ps in the S(1) state.
U2 - 10.1002/chem.201002928
DO - 10.1002/chem.201002928
M3 - Journal article
C2 - 21365700
VL - 17
SP - 3922
EP - 3931
JO - Chemistry: A European Journal
JF - Chemistry: A European Journal
SN - 0947-6539
IS - 14
ER -
ID: 33242870