Directing On‐Surface Reaction Pathways via Metal‐Organic Cu−N Coordination

Liang, Huifang; Xing, Shuaipeng; Shi, Zhenming; Zhang, Haiming; Chi, Lifeng

doi:10.1002/cphc.201901210

Cited by 9 publications

(14 citation statements)

References 37 publications

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“…This is due to the inductive effect resulting from the electron-withdrawing effect of the sp 2 -N atom. In our work, the −OH is also an electron-withdrawing group, likely giving rise to an inductive effect on ortho C–H bonds and facilitating their dissociation . (3) In the works of Fan et al and Huang et al, the C–H bond activation barrier could be lowered if its neighboring carbon sites become radicals on Cu(111).…”

Section: Results and Discussionmentioning

confidence: 79%

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Sequential Activation of Aromatic C─H Bonds on Cu(111)

et al. 2022

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avenue to prepare carbon-based nanomaterials. The emerging on-surface synthesis offers an unprecedented opportunity to achieve aromatic C−H activation on metal surfaces. Previous works mostly focus on the activation of either C−H bonds of phenyl rings or C−H bonds of functionalized aromatic rings. The research on the activation priority of two aromatic C−H bonds within a molecule has remained unreported. In this work, starting from a building block comprising both phenyl and phenol rings, we achieve the sequential activation of ortho C−H bonds of the phenol ring and meta C−H bonds of the phenyl ring on Cu(111) via stepwise annealing. During annealing, the hydrogen bond-and coordination interactionstabilized chiral nanostructures are observed successively below 450 K. At 450 K, covalent dimers and trimers originating from the activation of ortho C−H bonds of phenol ring are generated. Annealing to 500 K gives birth to the complex covalent polymers formed by the further activation of meta C−H bonds of phenyl ring. The morphologies of these nanostructures are resolved by scanning tunneling microscopy (STM). The synchrotron radiation photoemission spectroscopy (SRPES) is utilized to follow the chemical states of surface species during the reaction process. This work determines the activation priority of two aromatic C−H bonds. The attained principle could be potentially used to guide the hierarchical C−C coupling on metal surfaces.

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Section: Results and Discussionmentioning

confidence: 79%

“…In our work, the −OH is also an electron-withdrawing group, likely giving rise to an inductive effect on ortho C−H bonds and facilitating their dissociation. 59 (3) In the works of Fan et al 57…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Sequential Activation of Aromatic C─H Bonds on Cu(111)

et al. 2022

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“…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.…”

Section: Methodsmentioning

confidence: 99%

On‐Surface Synthesis of Giant Conjugated Macrocycles

Fan

Sun

et al. 2021

Angew Chem Int Ed

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We have achieved an on-surface synthesis of giant conjugated macrocycles having a diameter of % 7 nm and consisting of up to 30 subunits. The synthesis started with a debrominative coupling of the molecular precursors on a hot Ag(111) surface, leading to the formation of arched oligomeric chains and macrocycles. These products were revealed by scanning tunneling microscopy in combination with density functional theory to be covalent oligomers. These intermediates also display C-Ag organometallic bonds between parallel molecular subunits due to site-selective debromination and the asymmetric molecular conformation. Subsequent cyclodehydrogenation at higher temperatures steered the final conjugation of the macrocycles. Our findings provide a novel design strategy toward p-conjugated macrocycles and open up new opportunities for the precise synthesis of organic nanostructures.

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“…Among them, metal–organic coordination and H···F strong hydrogen bonding have been the two best investigated cases. First, a strong coordination between heteroatom-doped molecules and metals (e.g., Fe–N, Cu–N interaction) was reported to be efficient in confining molecular geometry, thus optimizing reaction pathways. , Second, as a typical reaction intermediate, organometallic compounds linked via C–metal–C could also play an important role in directing the molecular geometry for an intermolecular coupling reaction. − The formation of an organometallic intermediate makes the geometry of coupling motifs perfect for the following reaction. In this case, only a subtle transitional movement of active molecules is required after the removal of interstitial metal adatoms upon annealing, considerably increasing their collision probability.…”

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confidence: 99%

Steering On-Surface Reactions by Kinetic and Thermodynamic Strategies

Wang

Fan

Zhu

2023

J. Phys. Chem. Lett.

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Figure 1. (a) Adsorption geometry of the molecule (its chemical structure is inserted) used for the desulfonylation reaction on Ag(111) and Au(111), respectively, together with the energy barrier for each reaction. The STM image of the polyphenylene product on each surface is shown below. (b) Reaction scheme of DBBP and TBBP molecules on Ag(111). σ-radicals interacting with the substrate are marked by black dots. Corresponding STM images are displayed above or below each intermediate and product. The molecular adsorption model of TBBP on Ag(111) at 300 K is inserted in the corresponding STM image to better illustrate the adsorption structure. (c) Reaction scheme demonstrating chemisorptionpromoted C−H bond activation on Cu(111). The STM image of product 2 and nc-AFM image of product 5 are presented below.

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Directing On‐Surface Reaction Pathways via Metal‐Organic Cu−N Coordination

Cited by 9 publications

References 37 publications

Sequential Activation of Aromatic C─H Bonds on Cu(111)

Sequential Activation of Aromatic C─H Bonds on Cu(111)

On‐Surface Synthesis of Giant Conjugated Macrocycles

Steering On-Surface Reactions by Kinetic and Thermodynamic Strategies

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