On-Surface Cascade Reaction Based on Successive Debromination via Metal–Organic Coordination Template

Abstract

Precise control over on-surface covalent reaction pathways is crucial for engineering organic nanostructures with the single-atom precision. Herein, we demonstrate a step-by-step control of an on-surface cascade covalent reaction based on a successive debromination templated by noncovalent metal− organic coordination motifs. The molecular precursor is predesigned with different reactive sites and functional ligands, allowing for both chemical and structural tuning during on-surface reactions. Through the Fe-terpyridine template effect, we are able to direct the reaction to proceed in a three-step cascade pathway and finally to achieve a porous polyarylene nanoribbon structure. The approach opens new opportunities for construction of on-surface organic nanostructures in a predictable manner.

Variation of interaction zone size for the target design of 2D supramolecular networks

“…It was shown in the literature that the precise control over selectivity of on-surface reactions is crucial for the design of desired nanostructures. 32,33 Here we demonstrate that even slight variations of the size of the interaction zone drastically change the behavior of the systems considered. 34,35 We have found the rules governing the formation of diverse networks including Sierpinski triangles, Archimedean tessellation, Kagomé, and ladder networks.…”

On‐Surface Synthesis of Giant Conjugated Macrocycles

“…Overall, we note a selectivity of the intermolecular bonding motifs; that is, Py links with another Py through C−C bond exclusively, and the same does Qx (through C−Ag). This selectivity is presumably associated with a lower C−Br bond dissociation energy for Br−Py with respect to that for Br−Qx species [25, 29–31] . In addition, the standing‐up configuration of Pys induced by steric repulsion must play an important role.…”

Transformation of the coordination nanostructures of 4,4′,4′′-(1,3,5-triazine-2,4,6-triyl) tribenzoic acid molecules on HOPG triggered by the change in the concentration of metal ions

“…The coordination-driven molecular self-assembly of nanostructures on solid surfaces has attracted much attention owing to the potential applications of such structures in nanodevices and nanopatterning in the future. [1][2][3][4] Recently, coordination interaction has been used in the direct preparation of novel nanostructures ranging from clusters, 5,6 1D chains or polymers, [7][8][9][10] to 2D coordination frameworks, [11][12][13][14] and even 3D structures. [15][16][17] Moreover, their composition, morphology and properties have been well proved, and have opened up specic and targeted application in the areas of chemical and materials sciences.…”

“…A variety of studies have demonstrated the coordination nanostructures by altering organic ligands, such as carboxylate, 3,5,12,18 hydroxyl, 14,20,21 pyridine, 9,22–25 and triazine. 26–30 The triazine derivatives are important in a range of areas as ligands for supramolecular self-assembly of more complex mixed layers, hence it may be interesting to study the coordination properties of the triazine derivatives.…”