  In the search for novel organic charge transfer salts with variable charge
transfer degree we study the effects of two modifications to the recently
synthesized donor-acceptor Tetramethoxypyrene (TMP)-Tetracyanoquinodimethane
(TCNQ). One is of chemical nature by substituting the acceptor TCNQ molecules
by F4TCNQ molecules. The second consists in simulating the application of
uniaxial pressure along the stacking axis of the system. In order to test the
chemical substitution, we have grown single crystals of TMP-F4TCNQ and analyzed
its electronic structure via electronic transport measurements, ab initio
density functional theory (DFT) calculations and UV/VIS/IR absorption
spectroscopy. This system shows an almost ideal geometrical overlap of nearly
planar molecules alternately stacked (mixed stack) and this arrangement is
echoed by a semiconductor-like transport behavior with an increased
conductivity along the stacking direction. This is in contrast to TMP-TCNQ
which shows a less pronounced anisotropy and a smaller conductivity response.
Our bandstructure calculations confirm the one-dimensional behavior of
TMP-F4TCNQ with pro- nounced dispersion only along the stacking axis. Infrared
measurements illustrating the CN vibration frequency shift in F4TCNQ suggest
however no improvement on the degree of charge transfer in TMP-F4TCNQ with
respect to TMP-TCNQ. In both complexes about 0.1 is transferred from TMP to the
acceptor. Concerning the pressure effect, our DFT calculations on designed
TMP-TCNQ and TMP-F4TCNQ structures under different pressure conditions show
that application of uniaxial pressure along the stacking axis of TMP-TCNQ may
be the route to follow in order to obtain a much more pronounced charge
transfer.
