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Reported herein are the synthesis, electrochemical and structural characterization of wire-like Ru 2 -alkynyl compounds, Ru 2 ( ap ) 4 (L n ) x , where ap is 2-anilinopyridinate, and L n is –(C CC 6 H 4 ) n SCH 2 CH 2 SiMe 3 with n = 1 ( 1 ) and 2 ( 2 ), and x can be 1 ( a ) and 2 ( b ). Reactions between Ru 2 ( ap ) 4 Cl and one equiv. of LiL n yielded the mono-alkynyl compound only, while the use of 4–5 equiv. of LiL n resulted in a mixture of both the mono and bis-alkynyl species. Single crystal X-ray diffraction studies of compounds 1a and 1b revealed structural similarities to Ru 2 ( ap ) 4 (C 2 Ph) and Ru 2 ( ap ) 4 (C 2 Ph) 2 , respectively. Magnetic, spectroscopic and voltammetric measurements also revealed a minimal perturbation on electronic structures due to the functionalization of OPE ligands with thiol-TMSE group (–SCH 2 CH 2 SiMe 3 ). Most significantly, it can be estimated based on the structure of 1a that the Ru–OPE2–S– linkage in 2a is significantly longer than the depth of C11 thiol SAM and hence enables the insertion of 2a into the latter. |
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