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Single-molecule conductance determinations on HS(CH(2))(4)O(CH(2))(4)SH and HS(CH(2))(2)O(CH(2))(2)O(CH(2))(2)SH, and comparison with alkanedithiols of the same length.
MedLine Citation:
PMID:  22466424     Owner:  NLM     Status:  In-Data-Review    
The acetyl-protected, thiol-terminated ethers AcS(CH(2))(4)O(CH(2))(4)SAc and AcS(CH(2))(2)O(CH(2))(2)O(CH(2))(2)SAc have been synthesised, and a range of related scanning tunnelling microscopy (STM)-based methods have been employed to fabricate and electrically characterise gold | single molecule | gold junctions involving these molecules. The single-molecule conductance values obtained are consistently found to be substantially higher (by a factor of 2-3) than the conductances of analogous alkanedithiols of similar length (HS(CH(2))(9)SH and HS(CH(2))(8)SH, respectively). A rationalisation of these findings is suggested, namely that the lone pair electrons on the oxygen atoms are substantially closer in energy to the Fermi energy of the gold leads than are the occupied and unoccupied states of methylene chains, so that the ether oxygens behave in a manner analogous to 'wells' in a double-tunnelling-barrier system. In agreement with this suggestion, the current-voltage behaviour of the monoether can be fitted using the Simmons approach, and the barrier height is found to be significantly lower than for alkanedithiols of approximately the same length.
Lisa E Scullion; Edmund Leary; Simon J Higgins; Richard J Nichols
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Publication Detail:
Type:  Journal Article     Date:  2012-03-30
Journal Detail:
Title:  Journal of physics. Condensed matter : an Institute of Physics journal     Volume:  24     ISSN:  1361-648X     ISO Abbreviation:  J Phys Condens Matter     Publication Date:  2012 Apr 
Date Detail:
Created Date:  2012-04-02     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  101165248     Medline TA:  J Phys Condens Matter     Country:  England    
Other Details:
Languages:  eng     Pagination:  164211     Citation Subset:  IM    
Department of Chemistry, University of Liverpool, Crown Street, Liverpool L69 7ZD, UK.
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