Home > Research > Publications & Outputs > Detecting Mechanochemical Atropisomerization wi...

Links

Text available via DOI:

View graph of relations

Detecting Mechanochemical Atropisomerization within an STM Break Junction

Research output: Contribution to Journal/MagazineJournal articlepeer-review

Published

Standard

Detecting Mechanochemical Atropisomerization within an STM Break Junction. / Leary, Edmund; Roche, Cecile; Jiang, Hua-Wei et al.
In: Journal of the American Chemical Society, Vol. 140, No. 2, 17.01.2018, p. 710-718.

Research output: Contribution to Journal/MagazineJournal articlepeer-review

Harvard

Leary, E, Roche, C, Jiang, H-W, Grace, I, Teresa Gonzalez, M, Rubio-Bollinger, G, Romero-Muniz, C, Xiong, Y, Al-Galiby, Q, Noori, M, Lebedeva, MA, Porfyrakis, K, Agrait, N, Hodgson, A, Higgins, SJ, Lambert, CJ, Anderson, HL & Nichols, RJ 2018, 'Detecting Mechanochemical Atropisomerization within an STM Break Junction', Journal of the American Chemical Society, vol. 140, no. 2, pp. 710-718. https://doi.org/10.1021/jacs.7b10542

APA

Leary, E., Roche, C., Jiang, H-W., Grace, I., Teresa Gonzalez, M., Rubio-Bollinger, G., Romero-Muniz, C., Xiong, Y., Al-Galiby, Q., Noori, M., Lebedeva, M. A., Porfyrakis, K., Agrait, N., Hodgson, A., Higgins, S. J., Lambert, C. J., Anderson, H. L., & Nichols, R. J. (2018). Detecting Mechanochemical Atropisomerization within an STM Break Junction. Journal of the American Chemical Society, 140(2), 710-718. https://doi.org/10.1021/jacs.7b10542

Vancouver

Leary E, Roche C, Jiang H-W, Grace I, Teresa Gonzalez M, Rubio-Bollinger G et al. Detecting Mechanochemical Atropisomerization within an STM Break Junction. Journal of the American Chemical Society. 2018 Jan 17;140(2):710-718. Epub 2017 Dec 20. doi: 10.1021/jacs.7b10542

Author

Leary, Edmund ; Roche, Cecile ; Jiang, Hua-Wei et al. / Detecting Mechanochemical Atropisomerization within an STM Break Junction. In: Journal of the American Chemical Society. 2018 ; Vol. 140, No. 2. pp. 710-718.

Bibtex

@article{a7937661388847149f2183d419304912,
title = "Detecting Mechanochemical Atropisomerization within an STM Break Junction",
abstract = "We have employed the scanning tunneling microscope break-junction technique to investigate the single-molecule conductance of a family of 5,15-diaryl porphyrins bearing thioacetyl (SAc) or methylsulfide (SMe) binding groups at the ortho position of the phenyl rings (S2 compounds). These ortho substituents lead to two atropisomers, cis and trans, for each compound, which do not interconvert in solution under ambient conditions; even at high temperatures, isomerization takes several hours (half-life 15 h at 140 degrees C for SAc in C2Cl4D2). All the S2 compounds exhibit two conductance groups, and comparison with a monothiolated (S1) compound shows the higher group arises from a direct Au-Porphyrin interaction. The lower conductance group is associated with the S-to-S pathway. When the binding group is SMe, the difference in junction length distribution reflects the difference in S-S distance (0.3 nm) between the two isomers. In the case of SAc, there are no significant differences between the plateau length distributions of the two isomers, and both show maximal stretching distances well exceeding their calculated junction lengths. Contact deformation accounts for part of the extra length, but the results indicate that cis-to-trans conversion takes place in the junction for the cis isomer. The barrier to atropisomerization is lower than the strength of the thiolate Au-S and.Au-Au bonds, but higher than that of the Au- SMe bond, which explains why the strain in the junction only induces isomerization in the SAc compound.",
keywords = "SINGLE-MOLECULE JUNCTIONS, SENSITIZED SOLAR-CELLS, CHARGE-TRANSPORT, ELECTROMECHANICAL PROPERTIES, ANCHORING GROUPS, PORPHYRIN WIRES, CONDUCTANCE, DERIVATIVES, ELECTRONICS, PATHWAYS",
author = "Edmund Leary and Cecile Roche and Hua-Wei Jiang and Iain Grace and {Teresa Gonzalez}, M. and Gabino Rubio-Bollinger and Carlos Romero-Muniz and Yaoyao Xiong and Qusiy Al-Galiby and Mohammed Noori and Lebedeva, {Maria A.} and Kyriakos Porfyrakis and Nicolas Agrait and Andrew Hodgson and Higgins, {Simon J.} and Lambert, {Colin J.} and Anderson, {Harry L.} and Nichols, {Richard J.}",
year = "2018",
month = jan,
day = "17",
doi = "10.1021/jacs.7b10542",
language = "English",
volume = "140",
pages = "710--718",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "AMER CHEMICAL SOC",
number = "2",

}

RIS

TY - JOUR

T1 - Detecting Mechanochemical Atropisomerization within an STM Break Junction

AU - Leary, Edmund

AU - Roche, Cecile

AU - Jiang, Hua-Wei

AU - Grace, Iain

AU - Teresa Gonzalez, M.

AU - Rubio-Bollinger, Gabino

AU - Romero-Muniz, Carlos

AU - Xiong, Yaoyao

AU - Al-Galiby, Qusiy

AU - Noori, Mohammed

AU - Lebedeva, Maria A.

AU - Porfyrakis, Kyriakos

AU - Agrait, Nicolas

AU - Hodgson, Andrew

AU - Higgins, Simon J.

AU - Lambert, Colin J.

AU - Anderson, Harry L.

AU - Nichols, Richard J.

PY - 2018/1/17

Y1 - 2018/1/17

N2 - We have employed the scanning tunneling microscope break-junction technique to investigate the single-molecule conductance of a family of 5,15-diaryl porphyrins bearing thioacetyl (SAc) or methylsulfide (SMe) binding groups at the ortho position of the phenyl rings (S2 compounds). These ortho substituents lead to two atropisomers, cis and trans, for each compound, which do not interconvert in solution under ambient conditions; even at high temperatures, isomerization takes several hours (half-life 15 h at 140 degrees C for SAc in C2Cl4D2). All the S2 compounds exhibit two conductance groups, and comparison with a monothiolated (S1) compound shows the higher group arises from a direct Au-Porphyrin interaction. The lower conductance group is associated with the S-to-S pathway. When the binding group is SMe, the difference in junction length distribution reflects the difference in S-S distance (0.3 nm) between the two isomers. In the case of SAc, there are no significant differences between the plateau length distributions of the two isomers, and both show maximal stretching distances well exceeding their calculated junction lengths. Contact deformation accounts for part of the extra length, but the results indicate that cis-to-trans conversion takes place in the junction for the cis isomer. The barrier to atropisomerization is lower than the strength of the thiolate Au-S and.Au-Au bonds, but higher than that of the Au- SMe bond, which explains why the strain in the junction only induces isomerization in the SAc compound.

AB - We have employed the scanning tunneling microscope break-junction technique to investigate the single-molecule conductance of a family of 5,15-diaryl porphyrins bearing thioacetyl (SAc) or methylsulfide (SMe) binding groups at the ortho position of the phenyl rings (S2 compounds). These ortho substituents lead to two atropisomers, cis and trans, for each compound, which do not interconvert in solution under ambient conditions; even at high temperatures, isomerization takes several hours (half-life 15 h at 140 degrees C for SAc in C2Cl4D2). All the S2 compounds exhibit two conductance groups, and comparison with a monothiolated (S1) compound shows the higher group arises from a direct Au-Porphyrin interaction. The lower conductance group is associated with the S-to-S pathway. When the binding group is SMe, the difference in junction length distribution reflects the difference in S-S distance (0.3 nm) between the two isomers. In the case of SAc, there are no significant differences between the plateau length distributions of the two isomers, and both show maximal stretching distances well exceeding their calculated junction lengths. Contact deformation accounts for part of the extra length, but the results indicate that cis-to-trans conversion takes place in the junction for the cis isomer. The barrier to atropisomerization is lower than the strength of the thiolate Au-S and.Au-Au bonds, but higher than that of the Au- SMe bond, which explains why the strain in the junction only induces isomerization in the SAc compound.

KW - SINGLE-MOLECULE JUNCTIONS

KW - SENSITIZED SOLAR-CELLS

KW - CHARGE-TRANSPORT

KW - ELECTROMECHANICAL PROPERTIES

KW - ANCHORING GROUPS

KW - PORPHYRIN WIRES

KW - CONDUCTANCE

KW - DERIVATIVES

KW - ELECTRONICS

KW - PATHWAYS

U2 - 10.1021/jacs.7b10542

DO - 10.1021/jacs.7b10542

M3 - Journal article

VL - 140

SP - 710

EP - 718

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 2

ER -