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Research output: Contribution to Journal/Magazine › Journal article › peer-review
Research output: Contribution to Journal/Magazine › Journal article › peer-review
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TY - JOUR
T1 - Measuring the mechanical properties of molecular conformers
AU - Jarvis, S. P.
AU - Taylor, S.
AU - Baran, J. D.
AU - Champness, N. R.
AU - Larsson, J. A.
AU - Moriarty, P.
PY - 2015/9
Y1 - 2015/9
N2 - Scanning probe-actuated single molecule manipulation has proven to be an exceptionally powerful tool for the systematic atomic-scale interrogation of molecular adsorbates. To date, however, the extent to which molecular conformation affects the force required to push or pull a single molecule has not been explored. Here we probe the mechanochemical response of two tetra(4-bromophenyl) porphyrin conformers using non-contact atomic force microscopy where we find a large difference between the lateral forces required for manipulation. Remarkably, despite sharing very similar adsorption characteristics, variations in the potential energy surface are capable of prohibiting probe-induced positioning of one conformer, while simultaneously permitting manipulation of the alternative conformational form. Our results are interpreted in the context of dispersion-corrected density functional theory calculations which reveal significant differences in the diffusion barriers for each conformer. These results demonstrate that conformational variation significantly modifies the mechanical response of even simple porpyhrins, potentially affecting many other flexible molecules.
AB - Scanning probe-actuated single molecule manipulation has proven to be an exceptionally powerful tool for the systematic atomic-scale interrogation of molecular adsorbates. To date, however, the extent to which molecular conformation affects the force required to push or pull a single molecule has not been explored. Here we probe the mechanochemical response of two tetra(4-bromophenyl) porphyrin conformers using non-contact atomic force microscopy where we find a large difference between the lateral forces required for manipulation. Remarkably, despite sharing very similar adsorption characteristics, variations in the potential energy surface are capable of prohibiting probe-induced positioning of one conformer, while simultaneously permitting manipulation of the alternative conformational form. Our results are interpreted in the context of dispersion-corrected density functional theory calculations which reveal significant differences in the diffusion barriers for each conformer. These results demonstrate that conformational variation significantly modifies the mechanical response of even simple porpyhrins, potentially affecting many other flexible molecules.
KW - ATOMIC-FORCE MICROSCOPY
KW - MINIMUM ENERGY PATHS
KW - ELASTIC BAND METHOD
KW - SINGLE MOLECULES
KW - SADDLE-POINTS
KW - MANIPULATION
KW - PORPHYRINS
KW - CONFORMATION
KW - CONDUCTANCE
KW - ADSORPTION
U2 - 10.1038/ncomms9338
DO - 10.1038/ncomms9338
M3 - Journal article
VL - 6
JO - Nature Communications
JF - Nature Communications
SN - 2041-1723
M1 - 8338
ER -