Exploiting intermolecular interaction between alkyl-functionalised electron donor-acceptor pairs as a strategy to enhance electron transfer kinetics
Inseong Cho a, Peter Innis a, Attila Mozer a
a Intelligent Polymer Research Institute, University of Wollongong, Wollongong, 2522, Australia
Proceedings of International Conference on Hybrid and Organic Photovoltaics (HOPV19)
Roma, Italy, 2019 May 12th - 15th
Organizers: Prashant Kamat, Filippo De Angelis and Aldo Di Carlo
Poster, Inseong Cho, 057
Publication date: 11th February 2019

Understanding structural factors that affect the rate of electron transfer between surface bound molecules attached to a semiconductor surfaces and redox mediators in an electrolyte is vital to design the molecules of photovoltaic devices such as dye-sensitised solar cells and photoelectrosynthetic cells. However, the design of the molecules based on the structural factors without changes in driving force (∆G) is still not fully investigated. In particular, the extent to which insulating alkyl chains can block electron transfer has not been fully clarified yet. The open questions of this work was to what extent the insulating alkyl chains attached to dye molecules and/or redox mediators decrease the rate of electron transfer between electron donor–acceptor pairs. As opposed to our expectation, forward electron transfer rate determined by transient absorption was enhanced by up to 13 times without changes in ∆G when both the dye molecules and the redox mediators have long alkyl substitutions. We set a hypothesis based on the enhanced electron transfer rates, the enhancement is attributed to the intermolecular interaction between the redox mediators and the dye molecules. In order to test the hypothesis of the intermolecular interaction, three further experiments were conducted. The findings in this work suggest exploiting intermolecular interactions can be a fascinating strategy to enhance forward electron transfer when designing charge transfer interfaces of photovoltaic devices.

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