Temperature dependence of charge separation and recombination in XXXX oligomer-fullerene donor-acceptor systems.

@entity72977 @entity74 @entity12201 @entity7170
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 @entity72977 -linked @entity7170 oligomers (n = 1-4, 6) appended to @entity12201 were investigated. At room temperature, excitation of the @entity7170 oligomer led to fast (5-25 ps) electron transfer to @entity12201 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 (ii) 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 (  ). 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 @entity12201 -appended @entity7170 oligomers are suitable model systems for practical charge-separation devices such as bulk-heterojunction solar cells, where @entity74 strongly influences the electron-transfer reactions and performance of the device.
