Multiple electrochemically accessible colour states in surface-confined metal-organic monolayers: Stepwise embedding individual metal centres

Sequential covalent embedding of cobalt, osmium, and iron complexes of 4'-(pyridin-4-yl)-2,2':6',2''-terpyridine to surface-enhanced support pre-functionalized with a templating layer results in hetero-bimetallic (Os-Fe and Co-Fe) and hetero-trimetallic (Co-Os-Fe) monolayer materials....

Visible light-induced controlled surface grafting polymerization of hydroxyethyl methacrylate from isopropylthioxanthone semipinacol-terminated organic monolayers

Reaction scheme of the visible light-induced controlled surface grafting polymerization of methacrylate monomers onto organosilane-coated silicon initiated by previously coupled dormant ITXSP groups.

Organic monolayers disrupt plastic flow in metals

Adsorbed films often influence mechanical behavior of surfaces, leading to well-known mechanochemical phenomena such as liquid metal embrittlement and environment-assisted cracking. Here, we demonstrate a mechanochemical phenomenon wherein adsorbed long-chain organic monolayers disrupt large-strain plastic deformation in metals. Using high-speed in situ imaging and post facto analysis, we show that the monolayers induce a ductile-to-brittle transition. Sinuous flow, characteristic of ductile metals, gives way to quasi-periodic fracture, typical of brittle materials, with 85% reduction in deformation forces. By independently varying surface energy and molecule chain length via molecular self-assembly, we argue that this “embrittlement” is driven by adsorbate-induced surface stress, as against surface energy reduction. Our observations, backed by modeling and molecular simulations, could provide a basis for explaining diverse mechanochemical phenomena in solids. The results also have implications for manufacturing processes such as machining and comminution, and wear.