On-surface synthesis of a radical 2D supramolecular organic framework DOI Creative Commons
Ana Sánchez‐Grande, Federico Frezza, Adam Matěj

и другие.

Research Square (Research Square), Год журнала: 2023, Номер unknown

Опубликована: Сен. 26, 2023

Abstract The design of supramolecular organic radical cages and frameworks is one the main challenges in chemistry. Their interesting material properties wide applications make them very promising for (photo)redox catalysis, sensors, or host-guest spin-spin interactions. However, high reactivity systems makes such assemblies challenging. Here, we report on-surface synthesis a purely framework on Au(111). We combine chemistry to obtain two-dimensional hydrogen-bonded employ tripodal precursor, functionalized with 7-azaindole groups that, catalyzed by single gold atom surface, forms molecular product constituted π-extended fluoradene-based core. products self-assemble through hydrogen bonding, leading extended 2D domains ordered Kagome lattice. This approach demonstrates potential developing 2D-supramolecular

Язык: Английский

Separation of Halogen Atoms by Sodium from Dehalogenative Reactions on a Au(111) Surface DOI
Zhaoyu Zhang,

Yuhong Gao,

Zewei Yi

и другие.

ACS Nano, Год журнала: 2024, Номер 18(12), С. 9082 - 9091

Опубликована: Март 11, 2024

On-surface dehalogenative reactions have been promising in the construction of nanostructures with diverse morphologies and intriguing electronic properties, while halogen (X), as main byproduct, often impedes formation extended property characterization, reaction usually requires high C-X activation temperatures, especially on relatively inert Au(111). Enormous efforts precursor design, halogen-to-halide conversion, introduction extrinsic metal atoms devoted to either eliminating dissociated halogens or reducing barriers. However, it is still challenging separate from molecular systems facilitating under mild conditions. Herein, a versatile separation strategy has developed based sodium (Na) into Au(111) model that both isolates facilitates C-Br Moreover, combination scanning tunneling microscopy imaging density functional theory calculations reveals halides (NaX) these processes well reduction temperatures barriers, demonstrating versatility an effective "cleaner" "dehalogenator" surface halogens. Our study demonstrates valuable facilitate on-surface reactions, which will assist precise fabrication low-dimensional carbon nanostructures.

Язык: Английский

Процитировано

12
On-Surface Synthesis of a Radical 2D Supramolecular Organic Framework DOI Creative Commons
Federico Frezza, Adam Matěj, Ana Sánchez‐Grande

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(5), С. 3531 - 3538

Опубликована: Янв. 25, 2024

The design of supramolecular organic radical cages and frameworks is one the main challenges in chemistry. Their interesting material properties wide applications make them very promising for (photo)redox catalysis, sensors, or host–guest spin–spin interactions. However, high reactivity systems makes such assemblies challenging. Here, we report on-surface synthesis a purely framework on Au(111), by combining We employ tripodal precursor, functionalized with 7-azaindole groups that, catalyzed single gold atom surface, forms molecular product constituted π-extended fluoradene-based core. products self-assemble through hydrogen bonding, leading to extended 2D domains ordered Kagome-honeycomb lattice. This approach demonstrates potential developing

Язык: Английский

Процитировано

10
On‐Surface Synthesis of Non‐Benzenoid Nanographenes Embedding Azulene and Stone‐Wales Topologies DOI Creative Commons
Kalyan Biswas, Qifan Chen, Sebastian Obermann

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(13)

Опубликована: Фев. 1, 2024

Abstract The incorporation of non‐benzenoid motifs in graphene nanostructures significantly impacts their properties, making them attractive for applications carbon‐based electronics. However, understanding how specific structures influence properties remains limited, and further investigations are needed to fully comprehend implications. Here, we report an on‐surface synthetic strategy toward fabricating nanographenes containing different combinations pentagonal heptagonal rings. Their structure electronic were investigated via scanning tunneling microscopy spectroscopy, complemented by computational investigations. After thermal activation the precursor P on Au(111) surface, detected two major nanographene products. Nanographene A a−a embeds azulene units formed through oxidative ring‐closure methyl substituents, while a−s contains one unit Stone‐Wales defect, combination skeletal ring‐rearrangement reactions. exhibits antiferromagnetic ground state with highest magnetic exchange coupling reported up date a nanographene, coexisting side‐products closed shell configurations resulted from ring‐rearragement reactions ( B , s‐a s−s ). Our results provide insights into single gold atom assisted synthesis novel NGs tailored electronic/magnetic properties.

Язык: Английский

Процитировано

10
Surface Organic Nanostructures Mediated by Extrinsic Components: from Assembly to Reaction DOI Open Access
Chi Zhang,

Rujia Hou,

Wei Xu

и другие.

Small Methods, Год журнала: 2025, Номер unknown

Опубликована: Март 6, 2025

Surface organic nanostructures demonstrate great potential across multidisciplinary fields ranging from molecular electronics to energy conversion and storage. In the regime of surface chemistry, their preparation generally relies on intrinsic components originally involved in molecule-substrate systems drive assembly reaction. The recent paradigm shift employs extrinsic as functional mediators precisely regulate nanostructure formation pathways resulting nanostructures. This review highlights three categories modulators, including small gas molecules, metals, combinations, that allow construction modification through tailored addition, detailed roles regulatory mechanisms at single-molecule level are also discussed. emerging extrinsic-components-mediated reaction methodology displayed herein enriches toolbox for further allows physicochemical properties, opening new frontiers supramolecular engineering, nanomaterials development, etc.

Язык: Английский

Процитировано

1
Self-Limited Embedding Alternating 585-Ringed Divacancies and Metal Atoms into Graphene Nanoribbons DOI
Zhengya Wang,

Ruoting Yin,

Jie Meng

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(15), С. 8445 - 8454

Опубликована: Апрель 4, 2023

Because of their theoretically predicted intriguing properties, it is interesting to embed periodic 585-ringed divacancies into graphene nanoribbons (GNRs), but remains a great challenge. Here, we develop an on-surface cascade reaction from hydrogenated alternating and Ag atoms via intramolecular cyclodehydrogenation in seven-carbon-wide armchair GNR on the Ag(111) surface. Combining scanning tunneling microscopy/spectroscopy noncontact atomic force microscopy combined with first-principles calculations, in-situ-monitor evolution distinct structural electronic properties intermediates. The observation embedded further nudged elastic band calculations provide unambiguous evidence for adatom-mediated C–H activation pathway, where strain-induced self-limiting effect contributes formation superlattice atoms, which shows gap about 1.4 eV. Our findings open avenue introducing impurities single metal nonhexagonal rings synthesis, may novel route multifunctional nanostructures.

Язык: Английский

Процитировано

16
Competing pathways to aromaticity governed by amine dehydrogenation and metal-organic complexation in on-surface synthesis DOI Creative Commons

Andrés Lombana,

Songpol Chaunchaiyakul, Olivier Chuzel

и другие.

Chemical Science, Год журнала: 2025, Номер 16(7), С. 3198 - 3210

Опубликована: Янв. 1, 2025

Two distinct reaction pathways are observed on metal surfaces to preserve the dimer aromaticity.

Язык: Английский

Процитировано

0
Photogeneration and Visualization of a Surface‐Stabilized Dinitrene DOI Creative Commons
Federico Frezza, Ana Sánchez‐Grande, Sofia Canola

и другие.

Angewandte Chemie International Edition, Год журнала: 2025, Номер unknown

Опубликована: Март 6, 2025

Nitrenes are known as key intermediates in various chemical reactions. Nitrene transfer reactions particularly effective for synthesizing nitrogen-containing compounds, where metal catalysts play a crucial role controlling nitrene reactivity and selectivity. In this study, we demonstrate the formation of stable surface-supported dinitrene on Au(111) through UV irradiation its diazide precursor, characterized by scanning probe techniques. The photoreaction mechanism is elucidated with wavelength-dependent experiments time-dependent density functional theory calculations. Our findings present first real-space visualization adsorbed surface, highlighting potential catalysis surface functionalization.

Язык: Английский

Процитировано

0
On-Surface Reactions of Electronically Active Self-Assembled Monolayers for Electrode Work Function Tuning DOI Creative Commons
Ricardo Ruvalcaba, Zhongzhe Liu, Mohamad Insan Nugraha

и другие.

ACS Materials Letters, Год журнала: 2025, Номер unknown, С. 1421 - 1430

Опубликована: Март 19, 2025

Язык: Английский

Процитировано

0
Highly Selective On-Surface Ring-Opening of Aromatic Azulene Moiety DOI
Lulu Wang, Xinnan Peng, Jie Su

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 146(2), С. 1563 - 1571

Опубликована: Дек. 23, 2023

Controllable ring-opening of polycyclic aromatic hydrocarbons plays a crucial role in various chemical and biological processes. However, breaking down covalent C–C bonds is exceptionally challenging due to their high stability strong aromaticity. This study presents seminal report on the precise highly selective on-surface seven-membered ring within azulene moieties under mild conditions. The structures resulting products were identified using bond-resolved scanning probe microscopy. Furthermore, through density functional theory calculations, we uncovered mechanism behind process elucidated its driving force. key achieving this lies manipulating local aromaticity moiety strain-induced internal rearrangement cyclodehydrogenation. By precisely controlling these factors, successfully triggered desired reaction. Our findings not only provide valuable insights into but also open up new possibilities for manipulation reconstruction important structures.

Язык: Английский

Процитировано

5
On-surface synthesis of non-benzenoid conjugated polymers by selective atomic rearrangement of ethynylarenes DOI Creative Commons
Alejandro Jiménez-Martín, Federico Villalobos, Benjamín Mallada

и другие.

Chemical Science, Год журнала: 2022, Номер 14(6), С. 1403 - 1412

Опубликована: Дек. 20, 2022

Here, we report a new on-surface synthetic strategy to precisely introduce five-membered units into conjugated polymers from specifically designed precursor molecules that give rise low-bandgap fulvalene-bridged bisanthene polymers. The selective formation of non-benzenoid is finely controlled by the annealing parameters, which govern initiation atomic rearrangements efficiently transform previously formed diethynyl bridges fulvalene moieties. atomically precise structures and electronic properties have been unmistakably characterized STM, nc-AFM, STS results are supported DFT theoretical calculations. Interestingly, exhibit experimental narrow frontier gaps 1.2 eV on Au(111) with fully units. This can potentially be extended other tune their optoelectronic integrating rings at sites.

Язык: Английский

Процитировано

7