We present here a comprehensive study of the single molecule conductance of alkanes with carboxylic-acid
terminal groups, investigated with the I(s) and I(t) scanning tunneling microscopy (STM) methods. These
methods enable the formation of single molecular bridges between the gold substrate surface and gold STM
tip without the need to first form a metallic break junction. The I(s) and I(t) methods have up until this study
been used primarily with thiol head groups, and this current study shows that they can be extended to other
contact groups. The single molecule conductance of a series of dicarboxylic acids, HOOC−(CH2)
n
−COOH,
has been investigated as a function of length of the alkane chain (N = 4−12), temperature, pH, electrochemical
potential, and contact gap separation. The latter parameter, which has been often neglected in single molecule
conductance studies, is particularly noteworthy given the strong dependence of molecular conductance on
the separation between the STM tip and the surface. In this study, particular emphasis is put on determining
the contact gap spacing corresponding to the measured conductance values. Both molecular conductance and
the temperature dependence of molecular conductance are shown to depend significantly on contact gap
separation for these dicarboxylic acid-terminated molecular wires. Possible origins for this behavior are
discussed. Values for the tunneling decay constant, βN, and the contact resistance, A, have been determined
for the α,ω-dicarboxylic acid-terminated alkanes fully stretched in the contact junction (all-trans configuration).
βN values determined for this stretched configuration agree well with literature expectations, and the high
values for the contact resistance attest to a relatively poor coupling between the carboxylate end groups and
the Au contacts.
We have studied the ability of a novel molecule (diphenyl
bis(octadecylamino) phosphonium bromide)
to form both Langmuir films and Langmuir−Blodgett films under
different experimental conditions. It
has been found that this substance is capable of forming stable
monolayers at the air−water interface and
building up highly ordered LB films yielding Z-type LB films of high
quality (transfer ratio of 1) which
were characterized by UV−vis and IR spectra, electron microscopy, and
X-ray diffraction.
We present here the study of a symmetrically substituted viologen derivative, 1,1′-dioctadecyl 4,4′-bipyridinium salt, at the air-water interface and arranged in Langmuir-Blodgett (LB) films which were characterized using UV-vis spectroscopy. Detailed research of the electrochemical behavior of this molecule in LB films has been performed in terms of the nature of the counterion present in the water subphase, the number of layers, the transference pressure, and the nature of the electrolyte.
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