Magnetic Field and Temperature Dependencies Shed Light on the Recombination Kinetics of a Transition Metal Donor/Acceptor System

T. von Feilitzsch; P. Härter; Olav Schiemann; ME. Michel-Beyerle; UE Steiner; P. Gilch*

doi:10.1021/ja0547174

Magnetic Field and Temperature Dependencies Shed Light on the Recombination Kinetics of a Transition Metal Donor/Acceptor System

T. von Feilitzsch, P. Härter, Olav Schiemann, ME. Michel-Beyerle, UE Steiner, P. Gilch*

Research output: Contribution to journal › Article › peer-review

4 Citations (Scopus)

Abstract

The radical pair recombination of an intramolecular electron-transfer system containing a transition metal moiety has been addressed by femtosecond spectroscopy. The radical pair is formed by ultrafast electron transfer (90 fs) from a ferrocene residue to a photoexcited Nile blue moiety. Its recombination proceeds on the picosecond time scale in a multiexponential fashion. The kinetic pattern is a manifestation of spin processes competing with electron transfer. Magnetic field effects on these kinetics allow one to disentangle the two contributions. Their temperature dependencies yield the activation parameters of the two processes. The discussion focuses on the mechanism of electron spin relaxation. Strong evidence for the Orbach/Kivelson mechanism will be given.

Original language	English
Pages (from-to)	15228-15235
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	127
Issue number	43
DOIs	https://doi.org/10.1021/ja0547174
Publication status	Published - 2 Nov 2005

Keywords

SUBPICOSECOND TRANSIENT ABSORPTION
SPIN-LATTICE RELAXATION
ELECTRON-TRANSFER
FERROCENE
PHOTOOXIDATION
ACCEPTOR
COMPLEXES
MOLECULES
CHEMISTRY
MECHANISM

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10.1021/ja0547174

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title = "Magnetic Field and Temperature Dependencies Shed Light on the Recombination Kinetics of a Transition Metal Donor/Acceptor System",

abstract = "The radical pair recombination of an intramolecular electron-transfer system containing a transition metal moiety has been addressed by femtosecond spectroscopy. The radical pair is formed by ultrafast electron transfer (90 fs) from a ferrocene residue to a photoexcited Nile blue moiety. Its recombination proceeds on the picosecond time scale in a multiexponential fashion. The kinetic pattern is a manifestation of spin processes competing with electron transfer. Magnetic field effects on these kinetics allow one to disentangle the two contributions. Their temperature dependencies yield the activation parameters of the two processes. The discussion focuses on the mechanism of electron spin relaxation. Strong evidence for the Orbach/Kivelson mechanism will be given.",

keywords = "SUBPICOSECOND TRANSIENT ABSORPTION, SPIN-LATTICE RELAXATION, ELECTRON-TRANSFER, FERROCENE, PHOTOOXIDATION, ACCEPTOR, COMPLEXES, MOLECULES, CHEMISTRY, MECHANISM",

author = "{von Feilitzsch}, T. and P. H{\"a}rter and Olav Schiemann and ME. Michel-Beyerle and UE Steiner and P. Gilch*",

year = "2005",

month = nov,

day = "2",

doi = "10.1021/ja0547174",

language = "English",

volume = "127",

pages = "15228--15235",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society (ACS)",

number = "43",

}

TY - JOUR

T1 - Magnetic Field and Temperature Dependencies Shed Light on the Recombination Kinetics of a Transition Metal Donor/Acceptor System

AU - von Feilitzsch, T.

AU - Härter, P.

AU - Schiemann, Olav

AU - Michel-Beyerle, ME.

AU - Steiner, UE

AU - Gilch, P.

PY - 2005/11/2

Y1 - 2005/11/2

N2 - The radical pair recombination of an intramolecular electron-transfer system containing a transition metal moiety has been addressed by femtosecond spectroscopy. The radical pair is formed by ultrafast electron transfer (90 fs) from a ferrocene residue to a photoexcited Nile blue moiety. Its recombination proceeds on the picosecond time scale in a multiexponential fashion. The kinetic pattern is a manifestation of spin processes competing with electron transfer. Magnetic field effects on these kinetics allow one to disentangle the two contributions. Their temperature dependencies yield the activation parameters of the two processes. The discussion focuses on the mechanism of electron spin relaxation. Strong evidence for the Orbach/Kivelson mechanism will be given.

AB - The radical pair recombination of an intramolecular electron-transfer system containing a transition metal moiety has been addressed by femtosecond spectroscopy. The radical pair is formed by ultrafast electron transfer (90 fs) from a ferrocene residue to a photoexcited Nile blue moiety. Its recombination proceeds on the picosecond time scale in a multiexponential fashion. The kinetic pattern is a manifestation of spin processes competing with electron transfer. Magnetic field effects on these kinetics allow one to disentangle the two contributions. Their temperature dependencies yield the activation parameters of the two processes. The discussion focuses on the mechanism of electron spin relaxation. Strong evidence for the Orbach/Kivelson mechanism will be given.

KW - SUBPICOSECOND TRANSIENT ABSORPTION

KW - SPIN-LATTICE RELAXATION

KW - ELECTRON-TRANSFER

KW - FERROCENE

KW - PHOTOOXIDATION

KW - ACCEPTOR

KW - COMPLEXES

KW - MOLECULES

KW - CHEMISTRY

KW - MECHANISM

UR - http://www.scopus.com/inward/record.url?scp=27544491198&partnerID=8YFLogxK

UR - http://pubs.acs.org/cgi-bin/article.cgi/jacsat/2005/127/i43/pdf/ja0547174.pdf

U2 - 10.1021/ja0547174

DO - 10.1021/ja0547174

M3 - Article

SN - 0002-7863

VL - 127

SP - 15228

EP - 15235

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 43

ER -

Magnetic Field and Temperature Dependencies Shed Light on the Recombination Kinetics of a Transition Metal Donor/Acceptor System

Abstract

Keywords

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