Metallosupramolecular Assembly of Cr and p-Terphenyldinitrile by Dissociation of Metal Carbonyls on Au(111)

Abstract

Metal carbonyl complexes have been widely investigated for use in heterogeneous catalysis as a method for the formation of metal clusters. However, their use as a metal source for metallosupramolecular assemblies has not been widely considered. In this study, the combination of Cr­(CO)6 with p-terphenyldinitrile on Au(111) creates ordered 1D chains, which are thermally stable up to 423 K. The bond between the nitrile linkers and metal nodes undergoes a unique π-interaction, which thus far has been observed only in a small set of organometallic complexes. The structure and composition of the metal–organic coordination network have been elucidated and characterized using scanning tunnelling microscopy, high-resolution electron energy loss spectroscopy, and density functional theory calculations.

Bicomponent Supramolecular Architectures at the Vacuum–Solid Interface

“…Examples include, among many supramolecular surface nanostructures involving coordination bonds, Cr- p -terphenyldinitrile on Au(111), Fe-terephthalic acid on Cu(100), Fe-biphenolate and Co-dicarbonitrile on Ag(111), Fe- and Cu-trimesic acid on Cu(110), diiron-diterephthalate on Cu(100), Co-dicyanoazobenzene on Au(111), Co-dicarbonitrile-polyphenyl on Ag(111), Co-4,4′-(ethyne-1,2-diyl)­dibenzonitrile on Ag(111), Cu-1,3,8,10-tetraazaperopyrene on Cu(111), , Cu-thiolate on Cu(111), Mn-carboxylate on Au(111), Au-cyanosexiphenyl on Au(111) and the coordination between admolecules with alkali metals on Au(111), − Pb-tetracyanonaphtho-quinodimethane on Pb(111), and Cs atoms with aromatic carboxylic acids on Cu(100) . Moreover, the formation of isolated organometallic chains on Au(111) was observed with the deposition of iodine-functionalized units (2′,5′-diiodo-3,3″,5,5″-tetramethyl-1,1′:4′,1″-terphenyl) on the metallic surface induces the release of iodine and leads to bond formation between the molecule and diffusing gold adatoms.…”

Structure and Reactivity of Cu-doped Au(111) Surfaces

“…Nucleation of guest metals on Au(111) generally occurs via the place-exchange mechanism [5], which was initially ruled out for the adsorption of copper; however, it was later reported that the onset of copper adsorption does occur via a place-exchange mechanism, at specific sites identified as the narrowed regions within the highly reactive elbows of the Au(111)-(22× √ 3), irrespective of hcp or fcc stacking [1]. Other than for copper [6][7][8], this is also the case for other transition metals such as nickel [9][10][11][12], iron [13,14], and chromium [15,16], to name a few. Added clusters are regarded as a source of reactive metal atoms, over a surface commonly considered as a 2D inert support, opening up the possibility of modifying the reactivity of the Au(111) surface itself, via the formation of surface alloys, whereby both the added metal and gold are present in the top layer.…”

In Vacuo Porphyrin Metalation on Ag(111) via Chemical Vapor Deposition of Ru3(CO)12: Mechanistic Insights

“…12,13 More recently, CVD with metal carbonyl precursors was demonstrated to further provide a route for the on-surface one-dimensional supramolecular assembly of carbonitrile ditopic linker moleculers. 14 Our earlier multitechnique study demonstrated a selfteminating protocol, whereby following two cycles of exposure of a layer of the cyclodehydrogenated meso-tetraphenylporphyrin (4, 5, 6, 7, Figure 1) to the organometallic precursor molecule Ru 3 (CO) 12 (1) and subsequent annealing to 550 K, all free-base species transformed to ruthenium porphyrins without leaving byproducts (such as CO and excess Ru) on the surface. 10 Here, we elucidate the reaction pathway of this metalation method.…”

“…Porphyrins at interfaces, and in particular their electronic properties and their metalation, have been extensively studied. − On surfaces, the porphyrin metalation is most frequently achieved by physical vapor deposition of the desired metal atoms − or by capturing surface (ad)­atoms, the so-called “self-metalation”. , In an effort to metalate porphyrins on surfaces using metals with high sublimation temperature (e.g., Ru and Os) without being restricted by the supporting surface, we devised a different approach by employing metal–organic chemical vapor deposition (CVD) to metalate porphyrins on Ag(111) with trimetal dodecacarbonyls, , which are stable in air and thermally decompose on surfaces forming metal clusters. , More recently, CVD with metal carbonyl precursors was demonstrated to further provide a route for the on-surface one-dimensional supramolecular assembly of carbonitrile ditopic linker moleculers …”