Understanding structure-mobility relations for perylene tetracarboxydiimide derivatives.
Discotic mesophases are known for their ability to self-assemble into columnar structures and can serve as semiconducting molecular wires. Charge carrier mobility along these wires strongly depends on molecular packing, which is controlled by intermolecular interactions. By combining wide-angle X-ray scattering experiments with molecular dynamics simulations, we elucidate packing motifs of a perylene tetracarboxdiimide derivative, a task which is hard to achieve by using a single experimental or theoretical technique. We then relate the charge mobility to the molecular arrangement, both by pulse-radiolysis time-resolved microwave conductivity experiments and simulations based on the non-adiabatic Marcus charge transfer theory. Our results indicate that the helical molecular arrangement with the 45 degrees twist angle between the neighboring molecules favors hole transport in a compound normally considered as an n-type semiconductor. Statistical analysis shows that the transport is strongly suppressed by structural defects. By linking molecular packing and mobility, we eventually provide a pathway to the rational design of perylenediimide derivatives with high charge mobilities.
Marcon
Valentina
V
Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany. marcon@mpip-mainz.mpg.de
Breiby
Dag W
DW
Pisula
Wojciech
W
Dahl
Julie
J
Kirkpatrick
James
J
Patwardhan
Sameer
S
Grozema
Ferdinand
F
Andrienko
Denis
D