Linked Life Data

17107126

Source:http://linkedlifedata.com/resource/pubmed/id/17107126

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
46
pubmed:dateCreated
2006-11-19
pubmed:abstractText
The electron transfer to self-assembled molecular monolayers carrying a ferrocene (Fc) center, grafted on a flat Si(100) surface, is a recent subject of experimental investigation. We report here the density functional theory (DFT) ab initio calculation of Fc-silicon hybrid redox potentials. The systems were modeled with a slab of H-terminated Si(100) 1 x 1 and 2 x 1 surfaces: geometries were optimized using the ONIOM method, and solute-solvent interactions were included through the polarizable continuum model (PCM) method. Two new routes for Si functionalization with ethyl- (EtFC) and ethynyl-Fc (EFC) differing only in the unsaturation degree of the anchoring arm have been successfully explored, and the redox potential of the resulting hybrids has been measured by cyclic voltammetry: 0.675 and 0.851 V versus NHE for the EtFC and EFC derivatives, respectively. These values, along with the previously measured potential (0.700 V) for the mono-unsaturated derivative, vinyl-Fc, allow the relation between the unsaturation degree and the adduct redox potential to be studied. The comparison among the measured and computed potentials allows one to discriminate between different adduct isomers for the saturated species and more importantly provides strong indications that the carbon-carbon unsaturation initially present in the molecular arm used for anchoring to the surface is preserved upon addition, in contrast with the commonly accepted reaction mechanism.
pubmed:language
eng
pubmed:journal
pubmed:citationSubset
IM
pubmed:chemical
pubmed:status
MEDLINE
pubmed:month
Nov
pubmed:issn
1520-6106
pubmed:author
pubmed:issnType
Print
pubmed:day
23
pubmed:volume
110
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
22961-5
pubmed:dateRevised
2007-3-23
pubmed:meshHeading
pubmed:year
2006
pubmed:articleTitle
Measurement and DFT calculation of Fe(cp)(2) redox potential in molecular monolayers covalently bound to H-Si(100).
pubmed:publicationType
Journal Article, Comparative Study, Research Support, Non-U.S. Gov't