A comprehensive study of extended tetrathiafulvalene cruciform molecules for molecular electronics: synthesis and electrical transport measurements

Christian Richard Parker; Edmund Leary; Riccardo Frisenda; Zhongming Wei; Karsten Stein Jennum; Emil Glibstrup; Peter Bæch Abrahamsen; Marco Santella; Mikkel Andreas Christensen; Eduardo Antonio Della Pia; Tao Li; Maria Teresa Gonzalez; Xingbin Jiang; Thorbjørn Juul Morsing; Gabino Rubio-Bollinger; Bo Wegge Laursen; Kasper Nørgaard; Herre van der Zant; Nicolas Agrait; Mogens Brøndsted Nielsen

doi:10.1021/ja509937k

A comprehensive study of extended tetrathiafulvalene cruciform molecules for molecular electronics: synthesis and electrical transport measurements

Christian Richard Parker, Edmund Leary, Riccardo Frisenda, Zhongming Wei, Karsten Stein Jennum, Emil Glibstrup, Peter Bæch Abrahamsen, Marco Santella, Mikkel Andreas Christensen, Eduardo Antonio Della Pia, Tao Li, Maria Teresa Gonzalez, Xingbin Jiang, Thorbjørn Juul Morsing, Gabino Rubio-Bollinger, Bo Wegge Laursen, Kasper Nørgaard, Herre van der Zant, Nicolas Agrait, Mogens Brøndsted Nielsen

Department of Chemistry

37 Citations (Scopus)

Abstract

Cruciform-like molecules with two orthogonally placed π-conjugated systems have in recent years attracted significant interest for their potential use as molecular wires in molecular electronics. Here we present synthetic protocols for a large selection of cruciform molecules based on oligo(phenyleneethynylene) (OPE) and tetrathiafulvalene (TTF) scaffolds, end-capped with acetyl-protected thiolates as electrode anchoring groups. The molecules were subjected to a comprehensive study of their conducting properties as well as their photophysical and electrochemical properties in solution. The complex nature of the molecules and their possible binding in different configurations in junctions called for different techniques of conductance measurements: (1) conducting-probe atomic force microscopy (CP-AFM) measurements on self-assembled monolayers (SAMs), (2) mechanically controlled break-junction (MCBJ) measurements, and (3) scanning tunneling microscopy break-junction (STM-BJ) measurements. The CP-AFM measurements showed structure-property relationships from SAMs of series of OPE3 and OPE5 cruciform molecules; the conductance of the SAM increased with the number of dithiafulvene (DTF) units (0, 1, 2) along the wire, and it increased when substituting two arylethynyl end groups of the OPE3 backbone with two DTF units. The MCBJ and STM-BJ studies on single molecules both showed that DTFs decreased the junction formation probability, but, in contrast, no significant influence on the single-molecule conductance was observed. We suggest that the origins of the difference between SAM and single-molecule measurements lie in the nature of the molecule-electrode interface as well as in effects arising from molecular packing in the SAMs. This comprehensive study shows that for complex molecules care should be taken when directly comparing single-molecule measurements and measurements of SAMs and solid-state devices thereof.

Original language	English
Journal	Journal of the American Chemical Society
Volume	136
Issue number	47
Pages (from-to)	16497−16507
Number of pages	11
ISSN	0002-7863
DOIs	https://doi.org/10.1021/ja509937k
Publication status	Published - 26 Nov 2014

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10.1021/ja509937k

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Parker, C. R., Leary, E., Frisenda, R., Wei, Z., Jennum, K. S., Glibstrup, E., Abrahamsen, P. B., Santella, M., Christensen, M. A., Della Pia, E. A., Li, T., Gonzalez, M. T., Jiang, X., Morsing, T. J., Rubio-Bollinger, G., Laursen, B. W., Nørgaard, K., van der Zant, H., Agrait, N., & Nielsen, M. B. (2014). A comprehensive study of extended tetrathiafulvalene cruciform molecules for molecular electronics: synthesis and electrical transport measurements. Journal of the American Chemical Society, 136(47), 16497−16507. https://doi.org/10.1021/ja509937k

A comprehensive study of extended tetrathiafulvalene cruciform molecules for molecular electronics : synthesis and electrical transport measurements. / Parker, Christian Richard; Leary, Edmund; Frisenda, Riccardo et al.

In: Journal of the American Chemical Society, Vol. 136, No. 47, 26.11.2014, p. 16497−16507.

Research output: Contribution to journal › Journal article › Research › peer-review

Parker, CR, Leary, E, Frisenda, R, Wei, Z, Jennum, KS, Glibstrup, E, Abrahamsen, PB, Santella, M, Christensen, MA, Della Pia, EA, Li, T, Gonzalez, MT, Jiang, X, Morsing, TJ, Rubio-Bollinger, G, Laursen, BW, Nørgaard, K, van der Zant, H, Agrait, N & Nielsen, MB 2014, 'A comprehensive study of extended tetrathiafulvalene cruciform molecules for molecular electronics: synthesis and electrical transport measurements', Journal of the American Chemical Society, vol. 136, no. 47, pp. 16497−16507. https://doi.org/10.1021/ja509937k

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title = "A comprehensive study of extended tetrathiafulvalene cruciform molecules for molecular electronics: synthesis and electrical transport measurements",

abstract = "Cruciform-like molecules with two orthogonally placed π-conjugated systems have in recent years attracted significant interest for their potential use as molecular wires in molecular electronics. Here we present synthetic protocols for a large selection of cruciform molecules based on oligo(phenyleneethynylene) (OPE) and tetrathiafulvalene (TTF) scaffolds, end-capped with acetyl-protected thiolates as electrode anchoring groups. The molecules were subjected to a comprehensive study of their conducting properties as well as their photophysical and electrochemical properties in solution. The complex nature of the molecules and their possible binding in different configurations in junctions called for different techniques of conductance measurements: (1) conducting-probe atomic force microscopy (CP-AFM) measurements on self-assembled monolayers (SAMs), (2) mechanically controlled break-junction (MCBJ) measurements, and (3) scanning tunneling microscopy break-junction (STM-BJ) measurements. The CP-AFM measurements showed structure-property relationships from SAMs of series of OPE3 and OPE5 cruciform molecules; the conductance of the SAM increased with the number of dithiafulvene (DTF) units (0, 1, 2) along the wire, and it increased when substituting two arylethynyl end groups of the OPE3 backbone with two DTF units. The MCBJ and STM-BJ studies on single molecules both showed that DTFs decreased the junction formation probability, but, in contrast, no significant influence on the single-molecule conductance was observed. We suggest that the origins of the difference between SAM and single-molecule measurements lie in the nature of the molecule-electrode interface as well as in effects arising from molecular packing in the SAMs. This comprehensive study shows that for complex molecules care should be taken when directly comparing single-molecule measurements and measurements of SAMs and solid-state devices thereof.",

author = "Parker, {Christian Richard} and Edmund Leary and Riccardo Frisenda and Zhongming Wei and Jennum, {Karsten Stein} and Emil Glibstrup and Abrahamsen, {Peter B{\ae}ch} and Marco Santella and Christensen, {Mikkel Andreas} and {Della Pia}, {Eduardo Antonio} and Tao Li and Gonzalez, {Maria Teresa} and Xingbin Jiang and Morsing, {Thorbj{\o}rn Juul} and Gabino Rubio-Bollinger and Laursen, {Bo Wegge} and Kasper N{\o}rgaard and {van der Zant}, Herre and Nicolas Agrait and Nielsen, {Mogens Br{\o}ndsted}",

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T1 - A comprehensive study of extended tetrathiafulvalene cruciform molecules for molecular electronics

T2 - synthesis and electrical transport measurements

AU - Parker, Christian Richard

AU - Leary, Edmund

AU - Frisenda, Riccardo

AU - Wei, Zhongming

AU - Jennum, Karsten Stein

AU - Glibstrup, Emil

AU - Abrahamsen, Peter Bæch

AU - Santella, Marco

AU - Christensen, Mikkel Andreas

AU - Della Pia, Eduardo Antonio

AU - Li, Tao

AU - Gonzalez, Maria Teresa

AU - Jiang, Xingbin

AU - Morsing, Thorbjørn Juul

AU - Rubio-Bollinger, Gabino

AU - Laursen, Bo Wegge

AU - Nørgaard, Kasper

AU - van der Zant, Herre

AU - Agrait, Nicolas

AU - Nielsen, Mogens Brøndsted

PY - 2014/11/26

Y1 - 2014/11/26

N2 - Cruciform-like molecules with two orthogonally placed π-conjugated systems have in recent years attracted significant interest for their potential use as molecular wires in molecular electronics. Here we present synthetic protocols for a large selection of cruciform molecules based on oligo(phenyleneethynylene) (OPE) and tetrathiafulvalene (TTF) scaffolds, end-capped with acetyl-protected thiolates as electrode anchoring groups. The molecules were subjected to a comprehensive study of their conducting properties as well as their photophysical and electrochemical properties in solution. The complex nature of the molecules and their possible binding in different configurations in junctions called for different techniques of conductance measurements: (1) conducting-probe atomic force microscopy (CP-AFM) measurements on self-assembled monolayers (SAMs), (2) mechanically controlled break-junction (MCBJ) measurements, and (3) scanning tunneling microscopy break-junction (STM-BJ) measurements. The CP-AFM measurements showed structure-property relationships from SAMs of series of OPE3 and OPE5 cruciform molecules; the conductance of the SAM increased with the number of dithiafulvene (DTF) units (0, 1, 2) along the wire, and it increased when substituting two arylethynyl end groups of the OPE3 backbone with two DTF units. The MCBJ and STM-BJ studies on single molecules both showed that DTFs decreased the junction formation probability, but, in contrast, no significant influence on the single-molecule conductance was observed. We suggest that the origins of the difference between SAM and single-molecule measurements lie in the nature of the molecule-electrode interface as well as in effects arising from molecular packing in the SAMs. This comprehensive study shows that for complex molecules care should be taken when directly comparing single-molecule measurements and measurements of SAMs and solid-state devices thereof.

AB - Cruciform-like molecules with two orthogonally placed π-conjugated systems have in recent years attracted significant interest for their potential use as molecular wires in molecular electronics. Here we present synthetic protocols for a large selection of cruciform molecules based on oligo(phenyleneethynylene) (OPE) and tetrathiafulvalene (TTF) scaffolds, end-capped with acetyl-protected thiolates as electrode anchoring groups. The molecules were subjected to a comprehensive study of their conducting properties as well as their photophysical and electrochemical properties in solution. The complex nature of the molecules and their possible binding in different configurations in junctions called for different techniques of conductance measurements: (1) conducting-probe atomic force microscopy (CP-AFM) measurements on self-assembled monolayers (SAMs), (2) mechanically controlled break-junction (MCBJ) measurements, and (3) scanning tunneling microscopy break-junction (STM-BJ) measurements. The CP-AFM measurements showed structure-property relationships from SAMs of series of OPE3 and OPE5 cruciform molecules; the conductance of the SAM increased with the number of dithiafulvene (DTF) units (0, 1, 2) along the wire, and it increased when substituting two arylethynyl end groups of the OPE3 backbone with two DTF units. The MCBJ and STM-BJ studies on single molecules both showed that DTFs decreased the junction formation probability, but, in contrast, no significant influence on the single-molecule conductance was observed. We suggest that the origins of the difference between SAM and single-molecule measurements lie in the nature of the molecule-electrode interface as well as in effects arising from molecular packing in the SAMs. This comprehensive study shows that for complex molecules care should be taken when directly comparing single-molecule measurements and measurements of SAMs and solid-state devices thereof.

U2 - 10.1021/ja509937k

DO - 10.1021/ja509937k

M3 - Journal article

C2 - 25375316

SN - 0002-7863

VL - 136

SP - 16497−16507

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 47

ER -

A comprehensive study of extended tetrathiafulvalene cruciform molecules for molecular electronics: synthesis and electrical transport measurements

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