TY - JOUR
T1 - Molecular Junctions Inspired by Nature
T2 - Electrical Conduction through Noncovalent Nanobelts
AU - Jones, Leighton O.
AU - Mosquera, Martín A.
AU - Schatz, George C.
AU - Ratner, Mark A.
N1 - Funding Information:
L.O.J. and G.C.S. acknowledge support from Department of Energy, Office of Basic Energy Science, under Grant DE-SC0004752; M.A.M. and M.A.R. acknowledge support from the Department of Energy, Grant DE-AC02-06CH11357. This research was also supported in part through the computational resources and staff contributions provided for the Quest high performance computing facility at Northwestern University which is jointly supported by the Office of the Provost, the Office for Research, and Northwestern University Information Technology.
Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/9/26
Y1 - 2019/9/26
N2 - Charge transport occurs in a range of biomolecular systems, whose structures have covalent and noncovalent bonds. Understanding from these systems have yet to translate into molecular junction devices. We design junctions which have hydrogen-bonds between the edges of a series of prototype noncovalent nanobelts (NCNs) and vary the number of donor-acceptors to study their electrical properties. From frontier molecular orbitals (FMOs) and projected density of state (DOS) calculations, we found these NCN dimer junctions to have low HOMO-LUMO gaps and states at the Fermi level, suggesting these are metallic-like systems. Their conductance properties were studied with nonequilibrium Green's functions density functional theory (NEGF-DFT) and was found to decrease with cooperative H-bonding, that is, the conductance decreased as the alternating donor-acceptors around the nanobelts attenuates to a uniform distribution in the H-bonding arrays. The latter gave the highest conductance of 51.3 × 10-6 S and the Seebeck coefficient showed n-type (-36 to -39 μV K-1) behavior, while the lower conductors with alternating H-bonds are p-type (49.7 to 204 μV K-1). In addition, the NCNs have appreciable binding energies (19.8 to 46.1 kcal mol-1), implying they could form self-assembled monolayer (SAM) heterojunctions leading to a polymeric network for long-range charge transport.
AB - Charge transport occurs in a range of biomolecular systems, whose structures have covalent and noncovalent bonds. Understanding from these systems have yet to translate into molecular junction devices. We design junctions which have hydrogen-bonds between the edges of a series of prototype noncovalent nanobelts (NCNs) and vary the number of donor-acceptors to study their electrical properties. From frontier molecular orbitals (FMOs) and projected density of state (DOS) calculations, we found these NCN dimer junctions to have low HOMO-LUMO gaps and states at the Fermi level, suggesting these are metallic-like systems. Their conductance properties were studied with nonequilibrium Green's functions density functional theory (NEGF-DFT) and was found to decrease with cooperative H-bonding, that is, the conductance decreased as the alternating donor-acceptors around the nanobelts attenuates to a uniform distribution in the H-bonding arrays. The latter gave the highest conductance of 51.3 × 10-6 S and the Seebeck coefficient showed n-type (-36 to -39 μV K-1) behavior, while the lower conductors with alternating H-bonds are p-type (49.7 to 204 μV K-1). In addition, the NCNs have appreciable binding energies (19.8 to 46.1 kcal mol-1), implying they could form self-assembled monolayer (SAM) heterojunctions leading to a polymeric network for long-range charge transport.
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U2 - 10.1021/acs.jpcb.9b06255
DO - 10.1021/acs.jpcb.9b06255
M3 - Article
C2 - 31525929
AN - SCOPUS:85072687405
SN - 1520-6106
VL - 123
SP - 8096
EP - 8102
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
IS - 38
ER -