Electrochemical control of the single molecule conductance of a conjugated bis(pyrrolo)tetrathiafulvalene based molecular switch

Luke J. O'Driscoll, Joseph M. Hamill, Iain Grace, Bodil W. Nielsen, Eman Almutib, Yongchun Fu, Wenjing Hong, Colin J. Lambert, Jan O. Jeppesen*

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Resumé

As the field of unimolecular electronics develops, there is growing interest in the development of functionalised molecular wires, such as switches, which will allow for more complex molecular-scale circuits. To this end, a three redox state single molecule switch, 1, based on bis(pyrrolo)tetrathiafulvalene (BPTTF) has been designed, synthesised and investigated using scanning tunnelling microscopy break junction (STM-BJ) studies and quantum transport calculations. Oxidising the BPTTF unit increases its conjugation, which was anticipated to increase the molecular conductance of 1. By changing the redox state of 1 electrochemically it was possible to vary the single molecule conductance by more than an order of magnitude (from 10-5.2G0 to 10-3.8G0). Simulations afforded a qualitatively similar trend. An additional, higher conductance feature is present in most traces at junction sizes of around 2.0 nm-further extension affords the switchable lower conductance feature at junction sizes closer to the molecular length (ca. 3.0 nm). Analysis of the conductance traces shows that these two conductance features occur sequentially in nearly all junctions. This behaviour is attributed to an alternative initial junction conformation in which one or more of the BPTTF sulfur atoms acts as an anchoring group. This hypothesis is supported by a computational study of binding conformations and STM-BJ studies on a model compound, 2, with only one thiol anchor. Our results indicate that the redox properties of BPTTF make it an excellent candidate for use in single molecule switches.

OriginalsprogEngelsk
TidsskriftChemical Science
Vol/bind8
Udgave nummer9
Sider (fra-til)6123-6130
Antal sider8
ISSN2041-6520
DOI
StatusUdgivet - 2017

Fingeraftryk

Switches
Molecules
Scanning tunneling microscopy
Conformations
Anchors
Sulfur
Sulfhydryl Compounds
Electronic equipment
Wire
Atoms
tetrathiafulvalene
Networks (circuits)
Oxidation-Reduction

Citer dette

O'Driscoll, Luke J. ; Hamill, Joseph M. ; Grace, Iain ; Nielsen, Bodil W. ; Almutib, Eman ; Fu, Yongchun ; Hong, Wenjing ; Lambert, Colin J. ; Jeppesen, Jan O. / Electrochemical control of the single molecule conductance of a conjugated bis(pyrrolo)tetrathiafulvalene based molecular switch. I: Chemical Science. 2017 ; Bind 8, Nr. 9. s. 6123-6130.
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title = "Electrochemical control of the single molecule conductance of a conjugated bis(pyrrolo)tetrathiafulvalene based molecular switch",
abstract = "As the field of unimolecular electronics develops, there is growing interest in the development of functionalised molecular wires, such as switches, which will allow for more complex molecular-scale circuits. To this end, a three redox state single molecule switch, 1, based on bis(pyrrolo)tetrathiafulvalene (BPTTF) has been designed, synthesised and investigated using scanning tunnelling microscopy break junction (STM-BJ) studies and quantum transport calculations. Oxidising the BPTTF unit increases its conjugation, which was anticipated to increase the molecular conductance of 1. By changing the redox state of 1 electrochemically it was possible to vary the single molecule conductance by more than an order of magnitude (from 10-5.2G0 to 10-3.8G0). Simulations afforded a qualitatively similar trend. An additional, higher conductance feature is present in most traces at junction sizes of around 2.0 nm-further extension affords the switchable lower conductance feature at junction sizes closer to the molecular length (ca. 3.0 nm). Analysis of the conductance traces shows that these two conductance features occur sequentially in nearly all junctions. This behaviour is attributed to an alternative initial junction conformation in which one or more of the BPTTF sulfur atoms acts as an anchoring group. This hypothesis is supported by a computational study of binding conformations and STM-BJ studies on a model compound, 2, with only one thiol anchor. Our results indicate that the redox properties of BPTTF make it an excellent candidate for use in single molecule switches.",
author = "O'Driscoll, {Luke J.} and Hamill, {Joseph M.} and Iain Grace and Nielsen, {Bodil W.} and Eman Almutib and Yongchun Fu and Wenjing Hong and Lambert, {Colin J.} and Jeppesen, {Jan O.}",
year = "2017",
doi = "10.1039/c7sc02037f",
language = "English",
volume = "8",
pages = "6123--6130",
journal = "Chemical Science",
issn = "2041-6520",
publisher = "Royal Society of Chemistry",
number = "9",

}

O'Driscoll, LJ, Hamill, JM, Grace, I, Nielsen, BW, Almutib, E, Fu, Y, Hong, W, Lambert, CJ & Jeppesen, JO 2017, 'Electrochemical control of the single molecule conductance of a conjugated bis(pyrrolo)tetrathiafulvalene based molecular switch', Chemical Science, bind 8, nr. 9, s. 6123-6130. https://doi.org/10.1039/c7sc02037f

Electrochemical control of the single molecule conductance of a conjugated bis(pyrrolo)tetrathiafulvalene based molecular switch. / O'Driscoll, Luke J.; Hamill, Joseph M.; Grace, Iain; Nielsen, Bodil W.; Almutib, Eman; Fu, Yongchun; Hong, Wenjing; Lambert, Colin J.; Jeppesen, Jan O.

I: Chemical Science, Bind 8, Nr. 9, 2017, s. 6123-6130.

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

TY - JOUR

T1 - Electrochemical control of the single molecule conductance of a conjugated bis(pyrrolo)tetrathiafulvalene based molecular switch

AU - O'Driscoll, Luke J.

AU - Hamill, Joseph M.

AU - Grace, Iain

AU - Nielsen, Bodil W.

AU - Almutib, Eman

AU - Fu, Yongchun

AU - Hong, Wenjing

AU - Lambert, Colin J.

AU - Jeppesen, Jan O.

PY - 2017

Y1 - 2017

N2 - As the field of unimolecular electronics develops, there is growing interest in the development of functionalised molecular wires, such as switches, which will allow for more complex molecular-scale circuits. To this end, a three redox state single molecule switch, 1, based on bis(pyrrolo)tetrathiafulvalene (BPTTF) has been designed, synthesised and investigated using scanning tunnelling microscopy break junction (STM-BJ) studies and quantum transport calculations. Oxidising the BPTTF unit increases its conjugation, which was anticipated to increase the molecular conductance of 1. By changing the redox state of 1 electrochemically it was possible to vary the single molecule conductance by more than an order of magnitude (from 10-5.2G0 to 10-3.8G0). Simulations afforded a qualitatively similar trend. An additional, higher conductance feature is present in most traces at junction sizes of around 2.0 nm-further extension affords the switchable lower conductance feature at junction sizes closer to the molecular length (ca. 3.0 nm). Analysis of the conductance traces shows that these two conductance features occur sequentially in nearly all junctions. This behaviour is attributed to an alternative initial junction conformation in which one or more of the BPTTF sulfur atoms acts as an anchoring group. This hypothesis is supported by a computational study of binding conformations and STM-BJ studies on a model compound, 2, with only one thiol anchor. Our results indicate that the redox properties of BPTTF make it an excellent candidate for use in single molecule switches.

AB - As the field of unimolecular electronics develops, there is growing interest in the development of functionalised molecular wires, such as switches, which will allow for more complex molecular-scale circuits. To this end, a three redox state single molecule switch, 1, based on bis(pyrrolo)tetrathiafulvalene (BPTTF) has been designed, synthesised and investigated using scanning tunnelling microscopy break junction (STM-BJ) studies and quantum transport calculations. Oxidising the BPTTF unit increases its conjugation, which was anticipated to increase the molecular conductance of 1. By changing the redox state of 1 electrochemically it was possible to vary the single molecule conductance by more than an order of magnitude (from 10-5.2G0 to 10-3.8G0). Simulations afforded a qualitatively similar trend. An additional, higher conductance feature is present in most traces at junction sizes of around 2.0 nm-further extension affords the switchable lower conductance feature at junction sizes closer to the molecular length (ca. 3.0 nm). Analysis of the conductance traces shows that these two conductance features occur sequentially in nearly all junctions. This behaviour is attributed to an alternative initial junction conformation in which one or more of the BPTTF sulfur atoms acts as an anchoring group. This hypothesis is supported by a computational study of binding conformations and STM-BJ studies on a model compound, 2, with only one thiol anchor. Our results indicate that the redox properties of BPTTF make it an excellent candidate for use in single molecule switches.

U2 - 10.1039/c7sc02037f

DO - 10.1039/c7sc02037f

M3 - Journal article

VL - 8

SP - 6123

EP - 6130

JO - Chemical Science

JF - Chemical Science

SN - 2041-6520

IS - 9

ER -