Permethylation Introduces Destructive Quantum Interference in Saturated Silanes

TY - JOUR

T1 - Permethylation Introduces Destructive Quantum Interference in Saturated Silanes

AU - Garner, Marc H.

AU - Li, Haixing

AU - Neupane, Madhav

AU - Zou, Qi

AU - Liu, Taifeng

AU - Su, Timothy A.

AU - Shangguan, Zhichun

AU - Paley, Daniel W.

AU - Ng, Fay

AU - Xiao, Shengxiong

AU - Nuckolls, Colin

AU - Venkataraman, Latha

AU - Solomon, Gemma C.

PY - 2019/10/2

Y1 - 2019/10/2

N2 - The single-molecule conductance of silanes is suppressed due to destructive quantum interference in conformations with cisoid dihedral angles along the molecular backbone. Yet, despite the structural similarity, σ-interference effects have not been observed in alkanes. Here we report that the methyl substituents used in silanes are a prerequisite for σ-interference in these systems. Through density functional theory calculations, we find that the destructive interference is not evident to the same extent in nonmethylated silanes. We find the same is true in alkanes as the transmission is significantly suppressed in permethylated cyclic and bicyclic alkanes. Using scanning tunneling microscope break-junction method we determine the single-molecule conductance of functionalized cyclohexane and bicyclo[2.2.2]octane that are found to be higher than that of equivalent permethylated silanes. Rather than the difference between carbon and silicon atoms in the molecular backbones, our calculations reveal that it is primarily the difference between hydrogen and methyl substituents that result in the different electron transport properties of nonmethylated alkanes and permethylated silanes. Chemical substituents play an important role in determining the single-molecule conductance of saturated molecules, and this must be considered when we improve and expand the chemical design of insulating organic molecules.

AB - The single-molecule conductance of silanes is suppressed due to destructive quantum interference in conformations with cisoid dihedral angles along the molecular backbone. Yet, despite the structural similarity, σ-interference effects have not been observed in alkanes. Here we report that the methyl substituents used in silanes are a prerequisite for σ-interference in these systems. Through density functional theory calculations, we find that the destructive interference is not evident to the same extent in nonmethylated silanes. We find the same is true in alkanes as the transmission is significantly suppressed in permethylated cyclic and bicyclic alkanes. Using scanning tunneling microscope break-junction method we determine the single-molecule conductance of functionalized cyclohexane and bicyclo[2.2.2]octane that are found to be higher than that of equivalent permethylated silanes. Rather than the difference between carbon and silicon atoms in the molecular backbones, our calculations reveal that it is primarily the difference between hydrogen and methyl substituents that result in the different electron transport properties of nonmethylated alkanes and permethylated silanes. Chemical substituents play an important role in determining the single-molecule conductance of saturated molecules, and this must be considered when we improve and expand the chemical design of insulating organic molecules.

U2 - 10.1021/jacs.9b06965

DO - 10.1021/jacs.9b06965

M3 - Journal article

C2 - 31500410

SN - 0002-7863

VL - 141

SP - 15471

EP - 15476

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 39

ER -