Temperature Dependence of Charge Separation and Recombination in Porphyrin Oligomer-Fullerene Donor-Acceptor Systems
Journal article, 2011

Electron-transfer reactions are fundamental to many practical devices, but because of their complexity, it is often very difficult to interpret measurements done on the complete device. Therefore, studies of model systems are crucial. Here the rates of charge separation and recombination in donor acceptor systems consisting of a series of butadiyne-linked porphyrin oligomers (n = 1-4, 6) appended to C(60) were investigated. At room temperature, excitation of the porphyrin oligomer led to fast (5-25 ps) electron transfer to C(60) followed by slower (200-650 ps) recombination. The temperature dependence of the charge-separation reaction revealed a complex process for the longer oligomers, in which a combination of (i) direct charge separation and (4) migration of excitation energy along the oligomer followed by charge separation explained the observed fluorescence decay kinetics. The energy migration is controlled by the temperature-dependent conformational dynamics of the longer oligomers and thereby limits the quantum yield for charge separation. Charge recombination was also studied as a function of temperature through measurements of femtosecond transient absorption. The temperature dependence of the electron-transfer reactions could be successfully modeled using the Marcus equation through optimization of the electronic coupling (V) and the reorganization energy (lambda). For the charge-separation rate, all of the donor-acceptor systems could be successfully described by a common electronic coupling, supporting a model in which energy migration is followed by charge separation. In this respect, the C(60)-appended porphyrin oligomers are suitable model systems for practical charge-separation devices such as bulk-heterojunction solar cells, where conformational disorder strongly influences the electron-transfer reactions and performance of the device.

bacterial

dynamics

c-60

dyads

carbon nanotubes

excited-state

energy

photophysical properties

photosynthesis

walled

photoinduced electron-transfer

photosynthetic reaction centers

Author

Axel Kahnt

Chalmers, Chemical and Biological Engineering, Physical Chemistry

Joakim Kärnbratt

Chalmers, Chemical and Biological Engineering, Physical Chemistry

L. J. Esdaile

University of Oxford

M. Hutin

University of Oxford

K. Sawada

University of Oxford

Harry L. Anderson

University of Oxford

Bo Albinsson

Chalmers, Chemical and Biological Engineering, Physical Chemistry

Journal of the American Chemical Society

0002-7863 (ISSN) 1520-5126 (eISSN)

Vol. 133 25 9863-9871

Subject Categories

Chemical Sciences

DOI

10.1021/ja2019367

More information

Latest update

3/19/2018