Controlling a Chemical Coupling Reaction on a Surface: Tools and Strategies for On-Surface Synthesis

Abstract

On-surface synthesis is appearing as an extremely promising research field aimed at creating new organic materials. A large number of chemical reactions have been successfully demonstrated to take place directly on surfaces through unusual reaction mechanisms. In some cases the reaction conditions can be properly tuned to steer the formation of the reaction products. It is thus possible to control the initiation step of the reaction and its degree of advancement (the kinetics, the reaction yield); the nature of the reaction products (selectivity control, particularly in the case of competing processes); as well as the structure, position, and orientation of the covalent compounds, or the quality of the as-formed networks in terms of order and extension. The aim of our review is thus to provide an extensive description of all tools and strategies reported to date and to put them into perspective. We specifically define the different approaches available and group them into a few general categories. In the last part, we demonstrate the effective maturation of the on-surface synthesis field by reporting systems that are getting closer to application-relevant levels thanks to the use of advanced control strategies.

Strain‐Induced Isomerization in One‐Dimensional Metal–Organic Chains

“…[1][2][3][4][5][6] Ac ommon on-surface synthetic strategy involves thermal-or phototriggered chemical transformation of rationally designed molecular precursors on an appropriately chosen substrate. [7] Thef uture development in this field will hinge on the exploration of conceptually new toolkits that will enable precise steering of surface reactions under mild conditions to fabricate novel nanostructures with multiple functionalities.…”

Theoretical Modeling of the Surface‐Guided Self‐Assembly of Functional Molecules

“…Using this approach, very recently Judd and co‐workers have demonstrated the template‐directed self‐assembly and subsequent Ullmann coupling of 1,3,5‐tris(4‐iodophenyl)benzene inside porphyrin rings on Au(111) . Moreover, steering lateral organization of linear and branched guest molecules by means of specially designed corrals nanoshaved on covalently modified graphite has been shown with the STM technique at the liquid/solid interface …”

“…[14] Moreover, steering lateral organization of linear and branched guest molecules by means of specially designed corrals nanoshaved on covalently modified graphite has been shown with the STM technique at the liquid/solid interface. [15][16][17] Optimization of the on-surface template aiming at directing the self-assembly towards desired molecular structures is usually a difficult task which requires numerous test experiments. This is especially true for the guest molecules with multiple adsorbed conformations and/or several interaction centers.…”

Interfacial Synthesis of a Monolayered Fluorescent Two‐Dimensional Polymer through Dynamic Imine Chemistry

“…Two-dimensional polymers (2DPs) have been generally accepted as materials with atomic-thick or monolayer, covalently linked, highly ordered 2D topological network. [1][2][3][4][5][6][7][8] The recent high interest and the fast development of 2DPs materials are driven by their unique structures, [9][10][11] potential applications [12][13][14][15][16] and infinite structure possibilities through monomer design. [17] The properties of the 2DPs are completely different from those of traditional linear or branched polymers due to the total different 2D structure.…”