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High-quality SAMs could easily be assembled on Au based on two reliable and reproducible chemical assembly methods-base-promoted or acid-promoted method-and was characterized by ellipsometry and electrochemical techniques. See, for example: Cai, L.; Yao, Y.; Yang, J.; Price, D. W., Jr.; Tour, J. M. Chem. Mater. 2002, 14, 2905-2909 for detailed information.
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1542349569
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note
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+) = 0.424 V vs SCE. The supporting electrolyte, TBAPF6, was recrystallized twice and dried in a vacuum oven at 100 °C prior to transferring it into an inert-atmosphere drybox, where the EC measurements were carried out. Anhydrous MeCN or mixed MeCN/benzene was used as the solvents.
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Recent calculations performed by Seminario, J. M. and co-workers [see, for example, J. Am. Chem. Soc. 2002, 124, 10265] and also by Cornil, J. et al. [see, for example, J. Am. Chem. Soc. 2002, 124, 3516] have indeed shown that the actual geometry of the OPE wires can strongly affect the electrical properties of molecular junctions. Despite the fact that there is an almost free rotation around the triple bonds of OPE wires in the gas phase, the actual structure of the molecules in the SAMs investigated in our study is most likely planar since it is well-known that packing effects tend to reduce torsions along conjugated backbones. The choice of a planar conformation is further motivated by the fact that the electronic properties of conjugated systems are slightly affected by small deviations from planarity that are likely to occur in the SAMs (see, Brédas, J. L.; Street, G. B.; Thémans, B.; André, J. M. J. Chem. Phys. 1985, 83, 1323). Torsions could play a more significant role in experiments where a conjugated molecule is inserted into an inert matrix (as in ref 8) or when the whole monolayer is influenced by a static electric field (as in a nanopore), which could modulate cooperatively the torsion angles along the molecular wires.
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