Formation of Catalytic Metal-Molecule Contacts

Abstract

We describe a new strategy for the in situ growth of molecular wires predicated on the synthesis of a trifunctional "primed" contact formed from metal-carbon multiple bonds. The ruthenium-carbon pi bond provides structural stability to the molecular linkages under ambient conditions, and density functional calculations indicate the formation of an efficient conduit for charge carriers to pass between the metal and the molecule. Moreover, the metal-carbon pi bond provides a chemically reactive site from which a conjugated molecular wire can be grown in situ through an olefin metathesis reaction.

Olefin metathesis for metal incorporation: Preparation of conjugated ruthenium-containing complexes and polymers

“…Derivatives of the Grubbs first-generation catalyst (PCy 3 ) 2 C1 2 Ru@(CHPh), G1) including the Hoveyda-Grubbs catalyst [8], heterobimetallic complexes [9], and several different alkylidene complexes [10,11] have been prepared using this strategy. OMMI has also been reported in sulfur-rich Ru complexes [12] and on ruthenium surfaces [13]. Our efforts have been directed specifically at preparing conjugated complexes for the study of electronic properties and potential application in molecular electronics.…”

Hydrogen oxidation reaction on Pd(111) electrode in alkaline media: Ab-initio DFT study of OH effects

“…Recent developments in the abinitio density functional theory (DFT) calculations have allowed us to probe the adsorption phenomenon practically on any type of the electrode surface [6,18,19]. Many novel metallic surface properties such as nanoelectrode activity, quantum conductivity, docking molecule's orientation on the electrode surface, and collective behavior of various types of surface adsorbents can also be calculated with a high precision value by the DFT based atomistic simulations [20][21][22]. Besides, the DFT is also competent enough to effectively predict many diverse parameters of the electrolysis; the exact nature and role of the electrode material, role of electrolytic bath, reaction pathways, involved intermediates, etc.…”

High transmission in ruthenium–benzene–ruthenium molecular junctions

“…Tulevski et al observed stretching modes characteristic of a 1,4-disubstituted phenyl group after a fresh Ru surface reacts with 4-bromophenyldiazomethane [9], indicating that there should be no direct interactions between the benzene ring and the Ru surface. However the exact nature of the Ru-C multiple bonds is still unclear.…”

“…Therefore, in order to observe the intrinsic nature of conducting properties of benzene and other related conjugated molecules, a new kind of molecule-to-metal contact with an efficient channel for charge carriers is highly desired. Recently, the molecule-electrode contact formed by ruthenium-carbon (Ru-C) multiple bonds has been proposed to meet such a requirement [9]. Our previous calculations on the conductance of Ru-octeneRu molecular junctions demonstrated that the Ru-C p bond can continue the p conjugation of the conjugated molecule directly into the Ru electrodes thus a high conductance can be achieved [12].…”

“…For example, the transmission values of the gold-benzene dithiol-gold junction and the gold-benzene diamine-gold junction are reported to be 0.011 [4] and 0.0064 [6], respectively. This is due to the lack of an efficient conducting channel at the Au-S contact and the Au-N contact [8][9][10][11]. Therefore, in order to observe the intrinsic nature of conducting properties of benzene and other related conjugated molecules, a new kind of molecule-to-metal contact with an efficient channel for charge carriers is highly desired.…”