Interchain Interactions Mediated by Br Adsorbates in Arrays of Metal–Organic Hybrid Chains on Ag(111)

Abstract

Interchain interactions in arrays of metal–organic hybrid chains were studied using scanning tunneling microscopy and ab initio calculations. The array of hybrid chains having a Ag–anthryl biradical were self-assembled by catalytic scission of Br–C bonds in 9,10-dibromoanthracene on Ag(111). An atomic model for the observed chain structures was proposed. Ag atoms in chains were alternatingly located at hollow sites, making slightly zigzaging structures. Between the hybrid chains, Br atoms located at hollow sites to form Br···H intermolecular bonds. Anthryl biradicals had two different apparent heights; this was explained by considering Br···H intermolecular bonds and intrachain steric repulsion. When a hybrid chain was laterally moved by manipulation techniques, Br adsorbates moved together with the chain, implying that they are stabilized by Br···H intermolecular bonds.

Temperature-controlled metal/ligand stoichiometric ratio in Ag-TCNE coordination networks

“…Similar coordination networks with substrate adatoms have also been observed on other noble metal surfaces, such as Au(111), [5][6][7] Ag(110), 8 and Ag(111). 9,10 For silver and gold surfaces, the inclusion of the relatively unreactive surface adatoms into coordination networks is achieved by using very reactive molecules such as surface radicals arising from on-surface dehalogenation of halogenated compounds, [8][9][10] or very strong organic acceptors such as fluorinated tetracyanoquinodimethane (F4-TCNQ). 7 While the participation of adatoms arising from the metal surface facilitates the preparation of coordination networks, it also limits our ability to tune their physico-chemical properties.…”

“…Of course, using surface atoms as metal centers in coordination networks determines the chemical nature of the metal centers, but moreover the coordination networks with substrate adatoms reported so far in previous studies show a unique value for the metal/ligand stoichiometric ratio. [1][2][3][4][5][6][7][8][9][10] Actually, raising the temperature should enhance the availability of surface adatoms, thereby enabling the formation of coordination networks with different metal/ligand stoichiometries. Different metal/ligand stoichiometries have readily been observed by codepositing Fe atoms and carboxylic acid molecules in different relative amounts.…”

Steering Surface Reaction Dynamics with a Self‐Assembly Strategy: Ullmann Coupling on Metal Surfaces

“…[18][19][20][21] To date,t wo types of surface intermediates have been identified, [14] depending on how the aromatic species are bonded to surface metal atoms:1 )free-standing organometallic intermediates [22][23][24][25] and 2) surface-anchored aromatic species. TheUllmann coupling reaction is of great significance in constructing surface covalent nanostructures using halogen-containing aromatic derivatives.…”

“…[26][27][28][29][30] Ther eaction processes were carefully monitored by scanning tunneling microscopy (STM) at various coverages,r evealing that the Ullmann coupling reactions adopted different reaction pathways,a ss hown by the chemical equations in Figure 1a. [23,31,32] When warmed up to room temperature and subjected to as ufficient dwell period (ca. An individual BBP molecule is highlighted in the inset in Figure 1b,w hich displays an uneven, tadpole-like protrusion of the BBP molecule in the STM image.T he bright endpoint protrusion is due to the Br atom in the molecule.I nv arious clustered BBP aggregates (Figures 1b,f,a nd j), the molecules are held together by the halogen and weak hydrogen bond interactions.…”

Recent Progress in the Fabrication of Low Dimensional Nanostructures via Surface-Assisted Transforming and Coupling

“…Actually on Au surface, not obtaining organometallic intermediates is a common phenomenon, and the generally accepted opinion is that the SSR are mobile, diffuse around on the surface of substrate, and form covalent bonds upon encounter. On the contrary, the organometallic intermediates with C−M−C bonds are constantly obtained on Cu [16,[72][73][74] and Ag surfaces [75,76]. In a word, according to the explored experiments of Ullmann reaction, different experimental results can be briefly concluded in Table 1.…”