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Ultrafast Electron Transfer Dynamics of a Zn(II)porphyrin-Viologen Complex Revisited S-2 vs S-1 Reactions and Survival of Excess Excitation Energy
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Photochemistry and Molecular Science, Chemical Physics.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Photochemistry and Molecular Science, Chemical Physics.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Photochemistry and Molecular Science, Chemical Physics.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Photochemistry and Molecular Science, Chemical Physics.
2010 (English)In: Journal of Physical Chemistry B, ISSN 1520-6106, E-ISSN 1520-5207, Vol. 114, no 45, 14329-14338 p.Article in journal (Refereed) Published
Abstract [en]

The photoinduced electron transfer reactions in a self-assembled 1 1 complex of zinc(II)tetrasulphonatophe nylporphyrin (ZnTPPS4-) and methylviologen (MV2+) in aqueous solution were investigated with transient absorption spectroscopy ZnTPPS4- was excited either in the Soret or one of the two Q-bands corresponding to excitation into the S-2 and S-1 states respectively The resulting electron transfer to MV2+ occurred surprisingly with the same time constant of tau(FET) = 180 fs from both electronic states The subsequent back electron transfer was rapid and the kinetics was independent of the initially excited state (tau(BET) = 700 fs) However ground state reactants in a set of vibrationally excited states were observed The amount of vibrationally excited ground states detected increased with increasing energy of the initial excited state showing that excess excitation energy survived a two-step electron transfer reaction in solution Differences in the ZnTPSS3-/MV+. spectra suggest that the forward election transfer from the S-2 state at least partially produces an electronically excited charge transfer state which effectively suppresses the influence of the inverted regime Other possible reasons for the similar election transfer rates for the different excited states are also discussed

Place, publisher, year, edition, pages
2010. Vol. 114, no 45, 14329-14338 p.
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:uu:diva-139266DOI: 10.1021/jp9116867ISI: 000284018000026OAI: oai:DiVA.org:uu-139266DiVA: diva2:380924
Available from: 2010-12-22 Created: 2010-12-22 Last updated: 2017-12-11Bibliographically approved
In thesis
1. Ultrafast, Non-Equilibrium Electron Transfer Reactions of Molecular Complexes in Solution
Open this publication in new window or tab >>Ultrafast, Non-Equilibrium Electron Transfer Reactions of Molecular Complexes in Solution
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Photoinduced electron transfer is a fundamentally interesting process; it occurs everywhere in the natural world. Studies on electron transfer shed light on questions about the interaction between molecules and how the dynamics of these can be utilized to steer the electron transfer processes to achieve a desired goal. The goal may be to get electrons to the electrode of a solar cell, or to make the electrons form an energy rich fuel such as hydrogen, and it may also be an input or output for molecular switches. The importance of electron transfer reactions will be highlighted in this thesis, however, the main motivation is to gain a better understanding of the fundamental processes that affect the rate and direction of the electron transfer.

A study of photoinduced electron transfer (ET) in a series of metallophorphyrin/bipyridinium complexes in aqueous solution provided fresh insight concerning the intimate relationship between vibrational relaxation and electron transfer. The forward electron transfer from porphyrin to bipyridinium as well as the following back electron transfer to the ground state could be observed by femtosecond transient absorption spectroscopy. Both the reactant and the product states of the ET processes were vibrationally unrelaxed, in contrary to what is assumed for most expressions of the ET rates. This could be understood from the observation of unrelaxed ground states. The excess energy given by the initial excitation of the porphyrin does not relax completely during the two steps of electron transfer. This is an unusual observation, not reported in the literature prior the studies presented in this thesis. This study also gave the first clear evidence of electronically excited radical pairs formed as products of intramolecular electron transfer. Signs of electronically excited radical pairs were seen in transient spectra, and were further verified by the observation that the rates followed a Marcus normal region behavior for all excitation wavelengths, despite the relatively large excess energy of the second excited state.

This thesis also concerns electron transfer in solar cell dyes and mixed valence complexes. In the ruthenium polypyridyl complex Ru(dcb)2(NCS)2, where dcb = 4,4’-dicarboxy-2,2’-bipyridine, inter-ligand electron transfer (ILET) in the 3MLCT state was followed by means of femtosecond transient absorption anisotropy that was probed in the mid-IR region. Unexpectedly, ILET was not observed because electron density was localized on the same bpy during the time-window allowed by the rotational lifetime.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2014. 90 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1205
Keyword
electron transfer, laser, spectroscopy, transient absorption, anisortopy, inter ligand electron transfer, dye sensitized solar cell, DSSC, vibrational relaxation, ultrafast dynamics, fs spectroscopy
National Category
Chemical Sciences
Research subject
Chemistry with specialization in Chemical Physics
Identifiers
urn:nbn:se:uu:diva-235461 (URN)978-91-554-9107-9 (ISBN)
Public defence
2014-12-19, Häggsalen, Ångströmslaboratoriet, Lägerhyddsvägen 1, Uppsala, 10:15 (English)
Opponent
Supervisors
Available from: 2014-11-26 Created: 2014-11-03 Last updated: 2015-02-03

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