Journal of the American Chemical Society
Article
Schonenberger, C.; Calame, M. J. Am. Chem. Soc. 2008, 130, 1080−
1084.
(9) Newton, M. D.; Smalley, J. F. Phys. Chem. Chem. Phys. 2007, 9,
trace curves, whose evolution with electrode separation is
demonstrated for each molecular family in full movies. We
show further that the sliding of the anchor groups across the
pyramidal gold electrodes leads to oscillations in both the
electrical conductance and the junction energies of the
molecular wires. These conductance traces were used to
generate conductance histograms, which compare favorably
with the high-conductance regions of the experimental
histograms obtained from STM-BJ and MCBJ measurements.
To summarize, this study has shown that stable oligoynes
with up to eight acetylenic carbons in the backbone (i.e.,
tetraynes) can be synthesized with different end groups that are
suitable for anchoring the molecules to gold electrodes. BT
anchor groups are shown to be particularly beneficial in this
regard. Oligoynes are now established as a versatile class of π-
conjugated molecular wires for the fabrication of highly
conductive nanoscale junctions.
555−572.
(10) Liu, H. M.; Wang, N.; Zhao, J. W.; Guo, Y.; Yin, X.; Boey, F. Y.
C.; Zhang, H. ChemPhysChem 2008, 9, 1416−1424.
(11) Taylor, J.; Brandbyge, M.; Stokbro, K. Phys. Rev. B 2003, 68,
121101.
(12) James, D. K.; Tour, J. M. Chem. Mater. 2004, 16, 4423−4435.
(13) Kaliginedi, V.; Moreno-García, P.; Valkenier, H.; Hong, W.;
García-Suarez, V. M.; Buiter, P.; Otten, J. L. H.; Hummelen, J. C.;
́
Lambert, C. J.; Wandlowski, T. J. Am. Chem. Soc. 2012, 134, 5262−
5275.
(14) Tour, J. M. Acc. Chem. Res. 2000, 33, 791−804.
(15) Finch, C. M.; Sirichantaropass, S.; Bailey, S. W.; Grace, I. M.;
Garcia-Suarez, V. M.; Lambert, C. J. J. Phys.: Condens. Matter 2008, 20,
022203.
̌
́
(16) Crljen, Z.; Baranovic, G. Phys. Rev. Lett. 2007, 98, 116801.
(17) Garcia-Suarez, V. M.; Lambert, C. J. Nanotechnology 2008, 19,
455203.
ASSOCIATED CONTENT
* Supporting Information
(18) Gibtner, T.; Hampel, F.; Gisselbrecht, J.-P.; Hirsch, A. Chem.
■
S
Eur. J. 2002, 8, 408−432.
(19) Luu, T.; Elliott, E.; Slepkov, A. D.; Eisler, S.; McDonald, R.;
Hegmann, F. A.; Tykwinski, R. R. Org. Lett. 2004, 7, 51−54.
(20) Mohr, W.; Stahl, J.; Hampel, F.; Gladysz, J. A. Chem.Eur. J.
2003, 9, 3324−3340.
Experimental part: synthesis and characterization of oligoyne
compounds, UV−vis absorption and NMR spectra, X-ray
crystallography, stability tests, transport measurements and data
analysis procedures, conductance dependence on concentra-
tion. Computational part: simulation for isolated molecules,
length scale, electrical conductance and transmission curves of
molecules within junctions, movies of junction evolution. This
material is available free of charge via the Internet at http://
(21) Wang, C.; Batsanov, A. S.; West, K.; Bryce, M. R. Org. Lett.
2008, 10, 3069−3072.
(22) Klinger, C.; Vostrowsky, O.; Hirsch, A. Eur. J. Org. Chem. 2006,
1508−1524.
(23) Sugiyama, J.; Tomita, I. Eur. J. Org. Chem. 2007, 2007, 4651−
4653.
(24) Johnson, T. R.; Walton, D. R. M. Tetrahedron 1972, 28, 5221−
5236.
AUTHOR INFORMATION
Corresponding Author
■
(25) Simpkins, S. M. E.; Weller, M. D.; Cox, L. R. Chem. Commun.
2007, 4035−4037.
(26) Chalifoux, W. A.; Tykwinski, R. R. Nat. Chem. 2010, 2, 967−
971.
(27) Chen, F.; Hihath, J.; Huang, Z. F.; Li, X. L.; Tao, N. J. Annu. Rev.
Author Contributions
⊥These authors contributed equally.
Phys. Chem. 2007, 58, 535−564.
(28) Akkerman, H. B.; de Boer, B. J. Phys.: Cond. Matt 2008, 20,
013001.
(29) McCreery, R. L.; Bergren, A. J. Adv. Mater. 2009, 21, 4303−
4322.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
(30) Cuevas, J. C.; Scheer, E. Molecular Electronics: An Introduction to
Theory and Experiment; World Scientific Series in Nanoscience and
Nanotechnology; World Scientific: Singapore, 2010.
(31) Unimolecular and Supramolecular Electronics I in Topics in
Current Chemistry; Metzger, R. M. Ed.;Springer: New York, 2012.
(32) Chen, F.; Li, X. L.; Hihath, J.; Huang, Z. F.; Tao, N. J. J. Am.
Chem. Soc. 2006, 128, 15874−15881.
(33) Li, C.; Pobelov, I.; Wandlowski, T.; Bagrets, A.; Arnold, A.;
Evers, F. J. Am. Chem. Soc. 2008, 130, 318−326.
(34) Xu, B. Q.; Tao, N. J. J. Science 2003, 301, 1221−1223.
(35) Kamenetska, M.; Quek, S. Y.; Whalley, A. C.; Steigerwald, M. L.;
Choi, H. J.; Louie, S. G.; Nuckolls, C.; Hybertsen, M. S.; Neaton, J. B.;
Venkataraman, L. J. Am. Chem. Soc. 2010, 132, 6817−6821.
(36) Hong, W.; Manrique, D. Z.; Moreno-García, P.; Gulcur, M.;
Mishchenko, A.; Lambert, C. J.; Bryce, M. R.; Wandlowski, T. J. Am.
Chem. Soc. 2012, 134, 2292−2304.
■
This work was generously supported by the Swiss National
Science Foundation (200021-124643; NFP 62), the German
Science Foundation (priority program SPP 1243), the UK
EPSRC, the EC FP7 ITN “FUNMOLS” project no. 212942,
and the University of Bern. P.M.G. also acknowledges support
́
from CONACyT, Mexico (209297).
REFERENCES
■
(1) Acetylene Chemistry: Chemistry, Biology and Material Science;
Diederich, F., Stang, P. J., Tykwinski, R. R. , Eds.; Wiley-VCH:
Weinheim: Germany, 2005.
(2) Nielsen, M. B.; Diederich, F. Chem. Rev. 2005, 105, 1837−1868.
(3) Gholami, M.; Tykwinski, R. R. Chem. Rev. 2006, 106, 4997−
5027.
(37) Venkataraman, L.; Klare, J. E.; Tam, I. W.; Nuckolls, C.;
Hybertsen, M. S.; Steigerwald, M. L. Nano Lett. 2006, 6, 458−462.
(38) Ziessel, R.; Suffert, J.; Youinou, M.-T. J. Org. Chem. 1996, 61,
6535−6546.
(4) , Carbon-Rich Compounds: From Molecules to Materials; Haley, M.
M., Tykwinski, R. R., Eds.; Wiley- VCH: Weinheim, Germany, 2006.
(5) Szafert, S.; Gladysz, J. A. Chem. Rev. 2003, 103, 4175−4206.
(6) Slepkov, A. D.; Hegmann, F. A.; Eisler, S.; Elliott, E.; Tykwinski,
R. R. J. Chem. Phys. 2004, 120, 6807−6810.
(39) Wang, C. S.; Batsanov, A. S.; Bryce, M. R.; Martin, S.; Nichols,
R. J.; Higgins, S. J.; Garcia- Suarez, V. M.; Lambert, C. J. J. Am. Chem.
Soc. 2009, 131, 15647−15654.
́
(7) Cornil, J.; Beljonne, D.; Calbert, J. P.; Bredas, J. L. Adv. Mater.
2001, 13, 1053−1067.
(8) Huber, R.; Gonzalez, M. T.; Wu, S.; Langer, M.; Grunder, S.;
Horhoiu, V.; Mayor, M.; Bryce, M. R.; Wang, C. S.; Jitchati, R.;
(40) Ballmann, S.; Hieringer, W.; Secker, D.; Zheng, Q.; Gladysz, J.
A.; Gorling, A.; Weber, H. B. ChemPhysChem 2010, 11, 2256−2260.
̈
L
dx.doi.org/10.1021/ja4015293 | J. Am. Chem. Soc. XXXX, XXX, XXX−XXX