Synthesis, Electrochemistry, and Single-Molecule Conductance of Bimetallic 2,3,5,6-Tetra(pyridine-2-yl)pyrazine-Based...

The ligands 4'-(4-(methylthio)phenyl)-2,2':6',2″-terpyridine (L(1)), 4'-((4-(methylthio)phenyl)ethynyl)- 2,2':6',2″-terpyridine (L(2)), and bis(tridentate) bridging ligand 2,3,5,6-tetra(pyridine-2-yl)pyrazine (tpp) were used to prepare the complexes [Ru(L(1))2][PF6]2 ([1][PF6]2, [Ru(L(2))2][PF6]2 ([2][PF6]2), [{(L(1))Ru}(μ-tpp){Ru(L(1))}][PF6]4 ([3][PF6]4), and [{(L(2))Ru}(μ-tpp){Ru(L(2))}][PF6]4 ([4][PF6]4). Crystallographically determined structures give S···S distances of up to 32.0 Å in [4](4+). On the basis of electrochemical estimates, the highest occupied molecular orbitals of these complexes fall between -5.55 and -5.85 eV, close to the work function of clean gold (5.1-5.3 eV). The decay of conductance with molecular length across this series of molecules is approximately exponential, giving rise to a decay constant (pseudo β-value) of 1.5 nm(-1), falling between decay factors for oligoynes and oligophenylenes. The results are consistent with a tunnelling mechanism for the single-molecule conductance behavior.