A butadiyne-linked diruthenium molecular wire self-assembled on a gold electrode surface

Abstract

A 1,3-butadiyne-linked diruthenium complex 4 is successfully brought onto the gold surface in a lying flat mode to form self-assembled monolayers (SAMs) showing reversible multiple redox behaviors on the electrode surface. The diruthenium species with different oxidation states, particularly the Ru(2)(III,III) state which is unstable and impossible to isolate from the solution, can be detected by in situ IR spectroscopy.

Conformational Tuning of the Intramolecular Electronic Coupling in Molecular‐Wire Biruthenium Complexes Bridged by Biphenyl Derivatives

“…Compared with conventional IR spectra, in situ IR differential spectra can provide higher sensitivity and resolution for monitoring the course of a reaction and the existence of transient species or unstable intermediates 72. To better probe the character of these redox processes, in situ IR transmission differential spectra and conventional IR spectroscopic studies were carried out on complexes 4 a – e and 5 by using the ν (CO) band to evaluate the contributions of metal centers and bridging ligands to redox processes.…”

“…[72] To better probe the character of these redox processes, in situ IR transmission differential spectra and conventional IR spectroscopic studies were carried out on complexes 4a-e and 5 by using the n(CO) band to evaluatet he contributionso fm etal centers and bridging ligands to redox processes. The characteristic n(CO) vibrational frequencies for different redox states are listed in Table 4.…”

Grafting Single Molecule Magnets on Gold Nanoparticles

“…For the functionalization of Au NPs we used a tetrairon(III) complex with a propeller‐like structure, [Fe 4 (thioctic) 2 (dpm) 6 ] (Fe 4 ‐thioctic), where Hdpm is dipivaloylmethane and H 3 thioctic is a tripodal ligand obtained by esterification of (±)‐α‐lipoic acid (“thioctic acid”) with pentaerythritol (see Figure a). These cyclic disulfides derived from thioctic acid are known to interact strongly with metal surfaces and NPs . The two 1,2‐dithiolane rings located on opposite sides of the metal core indeed promote an efficient grafting of Fe 4 ‐thioctic on ultraflat gold substrates …”

Synthesis and Characterization of Novel 1,4‐Di(o‐thioaryl)benzene Buta‐1,3‐diynes

“…The compounds which consist of a conjugated π system as a bridging, as it will reveal the electrontransfer ability of the different bridging structures and thereby their potential as “molecular wires” between reducible subunits. And the compounds have the sulfur which can generate an Au−S bond with the gold, the character has realized the direct measurement of the electrochemical properties ,,…”

“…The 1, 3‐diyne system is attractive candidates for molecular wires. Sasaki groupsuccessfully synthesized a 1, 3‐butadiynelinked diruthenium complex and brought onto the gold surface in a lying flat mode to form self‐assembled monolayers showing reversible multiple redox behaviors on the electrode surface. Mayor et al have synthesized the 1, 4‐di(pentathiophenyl)phenyl‐buta‐1, 3‐diyne and its ability to transfer electrons from one reducible subunit to the other was investigated by electrochemical and spectroelectrochemical methods, and the results indicated the suitability of diacetylene connections as active electrontransfer linkers between molecular entities.…”