A Universal Method to Transform Aromatic Hydrocarbon Molecules into Confined Carbyne inside Single-Walled Carbon Nanotubes

ACS Nano, Год журнала: 2025, Номер unknown

Опубликована: Март 21, 2025

Carbyne, a sp1-hybridized allotrope of carbon, is linear carbon chain with exceptional theoretically predicted properties that surpass those sp2-hybridized graphene and nanotubes (CNTs). However, the existence carbyne has been debated due to its instability caused by Peierls distortion, which limits practical development. The only successful synthesis achieved inside CNTs, resulting in form known as confined (CC). CC can be synthesized multiwalled limiting property-tuning capabilities inner tubes CNTs. Here, we present universal method for synthesizing single-walled CNTs (SWCNTs) diameters 0.9–1.3 nm. Aromatic hydrocarbon molecules are filled SWCNTs subsequently transformed into under low-temperature annealing. A variety aromatic confirmed effective precursors formation CC, Raman frequencies centered around 1861 cm–1. Enriched (6,5) (7,6) less than 0.8 nm formation. Furthermore, resonance spectroscopy reveals optical band gap at cm–1 2.353 eV, consistent result obtained using relationship between frequency gap. This approach provides versatile route from various precursor diverse templates, not limited but could extend any templates appropriate size, including molecular sieves, zeolites, boron nitride nanotubes, metal–organic frameworks.

Язык: Английский

---

On-surface synthesis and characterization of linear and cyclic C6

Nature Synthesis, Год журнала: 2025, Номер unknown

Опубликована: Апрель 11, 2025

Язык: Английский

---

On-surface synthesis and characterization of anti-aromatic cyclo[12]carbon and cyclo[20]carbon

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Сен. 3, 2024

Cyclo[n]carbons have recently attracted significant attention owing to their geometric and electronic structures remaining largely unexplored in the condensed phase. In this work, we focus on two anti-aromatic cyclocarbons, namely C12 C20. By designing fully halogenated molecular precursors both including 4-numbered rings, further extend on-surface retro-Bergman ring-opening reaction, successfully produce The polyynic of C20 are unambiguously revealed by bond-resolved atomic force microscopy. More importantly, subtly positioning molecule into an fence formed Cl clusters allows us experimentally probe its frontier orbitals, yielding a transport gap 3.8 eV measured from scanning tunneling spectroscopy. Our work may advance field easier synthesis series cyclocarbons via strategy. Here, authors reaction

Язык: Английский

---

On‐Surface Covalent Synthesis of Carbon Nanomaterials by Harnessing Carbon gem‐Polyhalides

Advanced Materials, Год журнала: 2024, Номер 36(33)

Опубликована: Июнь 12, 2024

The design of innovative carbon-based nanostructures stands at the forefront both chemistry and materials science. In this context, π-conjugated compounds are great interest due to their impact in a variety fields, including optoelectronics, spintronics, energy storage, sensing catalysis. Despite extensive research efforts, substantial knowledge gaps persist synthesis characterization new with potential implications for science technology. On-surface has emerged as powerful discipline overcome limitations associated conventional solution methods, offering advanced tools characterize resulting nanomaterials. This review specifically highlights recent achievements utilization molecular precursors incorporating carbon geminal (gem)-polyhalides functional groups guide formation 0D species, well 1D, quasi-1D polymers, 2D nanoarchitectures. By delving into reaction pathways, novel structural designs, electronic, magnetic, topological features products, provides fundamental insights generation materials.

Язык: Английский

---

Distance and Voltage Dependence of Orbital Density Imaging Using a CO-Functionalized Tip in Scanning Tunneling Microscopy

ACS Nano, Год журнала: 2025, Номер unknown

Опубликована: Янв. 8, 2025

The appearance of frontier molecular ion resonances measured with scanning tunneling microscopy (STM)─often referred to as orbital density images─of single molecules was investigated using a CO-functionalized tip in dependence on bias voltage and tip–sample distance. As model systems, we studied pentacene naphthalocyanine bilayer NaCl Cu(111). Absolute distances were determined by means atomic force (AFM). STM imaging revealed transition from predominant p- s-wave contrast upon increasing the distance, but showed only small changes function voltage. distance-dependent change is explained steeper decay matrix element for between two p-wave centers, compared centers. In simulations fixed ratio s- states, can reproduce experimental data including contribution.

Язык: Английский

---

Synthesis and properties of confined carbyne and beyond

Advances in Colloid and Interface Science, Год журнала: 2025, Номер 342, С. 103519 - 103519

Опубликована: Апрель 11, 2025

Язык: Английский

---

Isomerization of Organometallic Polymers on Ag(111): Revealing the Intermolecular Hydrogen Transfer Mechanism

ACS Nano, Год журнала: 2025, Номер unknown

Опубликована: Апрель 23, 2025

Dehalogenation plays a crucial role in on-surface synthesis, but the bond-forming sites dehalogenation occasionally differ from original halogen-substituted sites, leading to unexpected products. Revealing its mechanism is essential for atomically precise fabrication of low-dimensional nanomaterials, although it remains elusive. Herein, we report an isomerization organometallic polymers derived debromination on Ag(111) and elucidate involving intermolecular hydrogen transfer via combining scanning tunneling microscopy, noncontact atomic force density functional theory calculations. At room temperature, precursor 1,4-bis(3-bromothiophen-2-yl)benzene undergoes surface-assisted Ag(111), forming two where correspond sites. Upon annealing 393 K, generates linear polymer, mismatched with Control experiments combined theoretical calculations demonstrate that proceeds through dissociation polymer chains into surface-stabilized diradical monomers or oligomers, transfer, final recombination radicals Ag adatoms.

Язык: Английский

---

On Surface Synthesis of Sp‐Hybridized Carbon Allotropes

Small Methods, Год журнала: 2025, Номер unknown

Опубликована: Апрель 21, 2025

Abstract Carbon allotropes have been extensively studied due to their unique structures and properties. exists in three hybridization states, among which sp‐hybridized carbon are particularly challenging synthesize high reactivity. On‐surface synthesis methods emerged as a promising approach for the generation characterization of such allotropes. In this review, recent experimental efforts summarized allotropes, including linear chains cyclo[ n ]carbons on surfaces.

Язык: Английский

---

Analysis of Interaction Features of Cyclo[13]carbon with Small Molecules and Formation Mechanism of Its Dimer

The Journal of Organic Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 29, 2024

The newly discovered cyclo[13]carbon, the first artificially synthesized odd-numbered carbon ring, is an intriguing isomer that provides a valuable subject for studying low-symmetry materials. In this work, we employed first-principles calculations to explore geometric structure and electronic properties of cyclo[13]carbon through various techniques such as vibrational mode analysis, bond order spin density electron localization electrostatic potential van der Waals visualization weak interactions, energy decomposition analysis. We investigated interaction characteristics with small molecules examined its dimer formation mechanism dynamics features using ab initio molecular dynamics. Our study reveals unique physicochemical novel ring system. antiaromaticity sets it apart from previously even-numbered rings, interactions playing crucial role in binding C13 dimers. This research theoretical insights complement experimental observations studies, aiding further investigation into diverse fresh material isomers promoting synthesis application materials electronics nanotechnology.

Язык: Английский

---

Coronene‐Based 2D Networks by On‐Surface Skeletal Rearrangement of Sumanene Precursors

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Авг. 28, 2024

The design of novel low-dimensional carbon materials is at the forefront modern chemistry. Recently, on-surface covalent synthesis has emerged as a powerful strategy to synthesize previously precluded compounds and polymers. Here, we report scanning probe microscopy study, complemented by theoretical calculations, on sequential skeletal rearrangement sumanene-based precursors into coronene-based organometallic network stepwise intra- inter-molecular reactions Au(111). Interestingly, upon higher annealing, formed networks evolve two-dimensional covalently linked patches through intermolecular homocoupling reactions. A new reaction mechanism proposed based role C-Au-C motifs promote two carbon-carbon couplings form cyclobutadiene bridges. Our results pave avenues for conversion molecular surfaces, affording unexplored materials.

Язык: Английский

---