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Title

Influence of the donor unit on the rectification ratio in tunnel junctions based on donor– acceptor SAMs using PTM units as acceptors

AuthorsSouto Salom, Manuel ; Díez-Cabanes, Valentin; Yuan, Li; Kyvik Ruiz, Adriana; Ratera, Immaculada ; Nijhuis, Christian A.; Corni, Jerome; Veciana, Jaume
KeywordsSelf-Assembled Monolayers
Donor-Acceptor
PTM radical
KPFM
Density Functional Theory (DFT) calculations
Issue Date28-Oct-2018
PublisherRoyal Society of Chemistry
CitationPhysical Chemistry Chemical Physics 20(40): 25638-25647 (2018)
AbstractDyads formed by an electron donor unit (D) covalently linked to an electron acceptor (A) by an organic bridge are promising materials as molecular rectifiers. Very recently, we have reported the charge transport measurements across self-assembled monolayers (SAMs) of two D–A systems consisting of the ferrocene (Fc) electron-donor linked to a polychlorotriphenylmethane (PTM) electron-acceptor in its non-radical (SAM 1) and radical (SAM 2) forms. Interestingly, we observed that the non-radical SAM 1 showed rectification behavior of 2 orders of magnitude higher than its radical analogue dyad 2. In order to study the influence of the donor unit on the transport properties, we report herein the synthesis and characterization of two new D–A SAMs in which the electron-donor Fc unit is replaced by a tetrathiafulvalene (TTF) moiety linked to the PTM unit in its non-radical (SAM 3) and radical (SAM 4) forms. The observed decrease in the rectification ratio and increased current density for TTF-PTM based SAMs 3 and 4 in comparison to Fc-PTM based SAMs 1 and 2 are explained, supported by theoretical calculations, by significant changes in the electronic and supramolecular structures.
Publisher version (URL)http://dx.doi.org/10.1039/c8cp05488f
URIhttp://hdl.handle.net/10261/174822
ISSN1463-9076
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