Conformations of cyclopentasilane stereoisomers control molecular junction conductance
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Conformations of cyclopentasilane stereoisomers control molecular junction conductance. / Li, Haixing; Garner, Marc Hamilton; Shangguan, Zhichun; Zheng, Qianwen; Su, Timothy A.; Neupane, Madhav; Li, Panpan; Velian, Alexandra; Steigerwald, Michael L.; Xiao, Shengxiong; Nuckolls, Colin; Solomon, Gemma C.; Venkataraman, Latha.
I: Chemical Science, Bind 7, Nr. 9, 2016, s. 5657-5662.Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
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TY - JOUR
T1 - Conformations of cyclopentasilane stereoisomers control molecular junction conductance
AU - Li, Haixing
AU - Garner, Marc Hamilton
AU - Shangguan, Zhichun
AU - Zheng, Qianwen
AU - Su, Timothy A.
AU - Neupane, Madhav
AU - Li, Panpan
AU - Velian, Alexandra
AU - Steigerwald, Michael L.
AU - Xiao, Shengxiong
AU - Nuckolls, Colin
AU - Solomon, Gemma C.
AU - Venkataraman, Latha
PY - 2016
Y1 - 2016
N2 - Here we examine the impact of ring conformation on the charge transport characteristics of cyclic pentasilane structures bound to gold electrodes in single molecule junctions. We investigate the conductance properties of alkylated cyclopentasilane cis and trans stereoisomers substituted in the 1,3-position with methylthiomethyl electrode binding groups using both the scanning tunneling microscope-based break junction technique and density functional theory based ab initio calculations. In contrast with the linear ones, these cyclic silanes yield lower conductance values; calculations reveal that the constrained dihedral geometries occurring within the ring are suboptimal for σ-orbital delocalization, and therefore, conductance. Theoretical calculations reproduce the measured conductance trends for both cis and trans isomers and find several distinct conformations that are likely to form stable molecular junctions at room temperature. Due to the weakened σ-conjugation in the molecule, through-space interactions are found to contribute significantly to the conductance. This manuscript details the vast conformational flexibility in cyclopentasilanes and the tremendous impact it has on controlling conductance.
AB - Here we examine the impact of ring conformation on the charge transport characteristics of cyclic pentasilane structures bound to gold electrodes in single molecule junctions. We investigate the conductance properties of alkylated cyclopentasilane cis and trans stereoisomers substituted in the 1,3-position with methylthiomethyl electrode binding groups using both the scanning tunneling microscope-based break junction technique and density functional theory based ab initio calculations. In contrast with the linear ones, these cyclic silanes yield lower conductance values; calculations reveal that the constrained dihedral geometries occurring within the ring are suboptimal for σ-orbital delocalization, and therefore, conductance. Theoretical calculations reproduce the measured conductance trends for both cis and trans isomers and find several distinct conformations that are likely to form stable molecular junctions at room temperature. Due to the weakened σ-conjugation in the molecule, through-space interactions are found to contribute significantly to the conductance. This manuscript details the vast conformational flexibility in cyclopentasilanes and the tremendous impact it has on controlling conductance.
U2 - 10.1039/c6sc01360k
DO - 10.1039/c6sc01360k
M3 - Journal article
AN - SCOPUS:84983591629
VL - 7
SP - 5657
EP - 5662
JO - Chemical Science
JF - Chemical Science
SN - 2041-6520
IS - 9
ER -
ID: 166006575