Single-molecule conductance determinations on HS(CH2)4O(CH2)4SH and HS(CH2)2O(CH2)2O(CH2)2SH, and comparison with alkanedithiols of the same length.

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.

Anomalous length and voltage dependence of single molecule conductance.

A systematic experimental study of the electrical conductance of single alkanedithiol molecules (HS-(CH(2))(N)-SH) between gold contacts in air for N = 3-12 is presented. For all of these molecules, three different fundamental conductance groups (low, medium and high conductance) were observed. For long molecules (N > 7) the conductance decays exponentially with molecular length for all three conductance groups, as it has been reported previously.