Large Variations in the Single-Molecule Conductance of Cyclic and Bicyclic Silanes

Haixing Li; Marc H. Garner; Zhichun Shangguan; Yan Chen; Qianwen Zheng; Timothy A. Su; Madhav Neupane; Taifeng Liu; Michael L. Steigerwald; Fay Ng; Colin Nuckolls; Shengxiong Xiao; Gemma C. Solomon; Latha Venkataraman

doi:10.1021/jacs.8b10296

Large Variations in the Single-Molecule Conductance of Cyclic and Bicyclic Silanes

Haixing Li, Marc H. Garner, Zhichun Shangguan, Yan Chen, Qianwen Zheng, Timothy A. Su, Madhav Neupane, Taifeng Liu, Michael L. Steigerwald, Fay Ng, Colin Nuckolls, Shengxiong Xiao, Gemma C. Solomon, Latha Venkataraman

Department of Chemistry

13 Citations (Scopus)

Abstract

Linear silanes are efficient molecular wires due to strong σ-conjugation in the transoid conformation; however, the structure-function relationship for the conformational dependence of the single-molecule conductance of silanes remains untested. Here we report the syntheses, electrical measurements, and theoretical characterization of four series of functionalized cyclic and bicyclic silanes including a cyclotetrasilane, a cyclopentasilane, a bicyclo[2.2.1]heptasilane, and a bicyclo[2.2.2]octasilane, which are all extended by linear silicon linkers of varying length. We find an unusual variation of the single-molecule conductance among the four series at each linker length. We determine the relative conductance of the (bi)cyclic silicon structures by using the common length dependence of the four series rather than comparing the conductance at a single length. In contrast with the cyclic π-conjugated molecules, the conductance of σ-conjugated (bi)cyclic silanes is dominated by a single path through the molecule and is controlled by the dihedral angles along this path. This strong sensitivity to molecular conformation dictates the single-molecule conductance of σ-conjugated silanes and allows for systematic control of the conductance through molecular design.

Original language	English
Journal	Journal of the American Chemical Society
Volume	140
Issue number	44
Pages (from-to)	15080-15088
Number of pages	8
ISSN	0002-7863
DOIs	https://doi.org/10.1021/jacs.8b10296
Publication status	Published - 7 Nov 2018

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Li, H., Garner, M. H., Shangguan, Z., Chen, Y., Zheng, Q., Su, T. A., Neupane, M., Liu, T., Steigerwald, M. L., Ng, F., Nuckolls, C., Xiao, S., Solomon, G. C., & Venkataraman, L. (2018). Large Variations in the Single-Molecule Conductance of Cyclic and Bicyclic Silanes. Journal of the American Chemical Society, 140(44), 15080-15088. https://doi.org/10.1021/jacs.8b10296

@article{65ca8eebb9e64baebe23e78fcc8d35ba,

title = "Large Variations in the Single-Molecule Conductance of Cyclic and Bicyclic Silanes",

abstract = "Linear silanes are efficient molecular wires due to strong σ-conjugation in the transoid conformation; however, the structure-function relationship for the conformational dependence of the single-molecule conductance of silanes remains untested. Here we report the syntheses, electrical measurements, and theoretical characterization of four series of functionalized cyclic and bicyclic silanes including a cyclotetrasilane, a cyclopentasilane, a bicyclo[2.2.1]heptasilane, and a bicyclo[2.2.2]octasilane, which are all extended by linear silicon linkers of varying length. We find an unusual variation of the single-molecule conductance among the four series at each linker length. We determine the relative conductance of the (bi)cyclic silicon structures by using the common length dependence of the four series rather than comparing the conductance at a single length. In contrast with the cyclic π-conjugated molecules, the conductance of σ-conjugated (bi)cyclic silanes is dominated by a single path through the molecule and is controlled by the dihedral angles along this path. This strong sensitivity to molecular conformation dictates the single-molecule conductance of σ-conjugated silanes and allows for systematic control of the conductance through molecular design.",

author = "Haixing Li and Garner, {Marc H.} and Zhichun Shangguan and Yan Chen and Qianwen Zheng and Su, {Timothy A.} and Madhav Neupane and Taifeng Liu and Steigerwald, {Michael L.} and Fay Ng and Colin Nuckolls and Shengxiong Xiao and Solomon, {Gemma C.} and Latha Venkataraman",

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T1 - Large Variations in the Single-Molecule Conductance of Cyclic and Bicyclic Silanes

AU - Li, Haixing

AU - Garner, Marc H.

AU - Shangguan, Zhichun

AU - Chen, Yan

AU - Zheng, Qianwen

AU - Su, Timothy A.

AU - Neupane, Madhav

AU - Liu, Taifeng

AU - Steigerwald, Michael L.

AU - Ng, Fay

AU - Nuckolls, Colin

AU - Xiao, Shengxiong

AU - Solomon, Gemma C.

AU - Venkataraman, Latha

PY - 2018/11/7

Y1 - 2018/11/7

N2 - Linear silanes are efficient molecular wires due to strong σ-conjugation in the transoid conformation; however, the structure-function relationship for the conformational dependence of the single-molecule conductance of silanes remains untested. Here we report the syntheses, electrical measurements, and theoretical characterization of four series of functionalized cyclic and bicyclic silanes including a cyclotetrasilane, a cyclopentasilane, a bicyclo[2.2.1]heptasilane, and a bicyclo[2.2.2]octasilane, which are all extended by linear silicon linkers of varying length. We find an unusual variation of the single-molecule conductance among the four series at each linker length. We determine the relative conductance of the (bi)cyclic silicon structures by using the common length dependence of the four series rather than comparing the conductance at a single length. In contrast with the cyclic π-conjugated molecules, the conductance of σ-conjugated (bi)cyclic silanes is dominated by a single path through the molecule and is controlled by the dihedral angles along this path. This strong sensitivity to molecular conformation dictates the single-molecule conductance of σ-conjugated silanes and allows for systematic control of the conductance through molecular design.

AB - Linear silanes are efficient molecular wires due to strong σ-conjugation in the transoid conformation; however, the structure-function relationship for the conformational dependence of the single-molecule conductance of silanes remains untested. Here we report the syntheses, electrical measurements, and theoretical characterization of four series of functionalized cyclic and bicyclic silanes including a cyclotetrasilane, a cyclopentasilane, a bicyclo[2.2.1]heptasilane, and a bicyclo[2.2.2]octasilane, which are all extended by linear silicon linkers of varying length. We find an unusual variation of the single-molecule conductance among the four series at each linker length. We determine the relative conductance of the (bi)cyclic silicon structures by using the common length dependence of the four series rather than comparing the conductance at a single length. In contrast with the cyclic π-conjugated molecules, the conductance of σ-conjugated (bi)cyclic silanes is dominated by a single path through the molecule and is controlled by the dihedral angles along this path. This strong sensitivity to molecular conformation dictates the single-molecule conductance of σ-conjugated silanes and allows for systematic control of the conductance through molecular design.

U2 - 10.1021/jacs.8b10296

DO - 10.1021/jacs.8b10296

M3 - Journal article

C2 - 30372051

SN - 0002-7863

VL - 140

SP - 15080

EP - 15088

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 44

ER -

Large Variations in the Single-Molecule Conductance of Cyclic and Bicyclic Silanes

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