Orbital magnetic susceptibility of zigzag carbon nanobelts: a tight-binding study DOI
Norio Inui

Journal of Physics Condensed Matter, Journal Year: 2024, Volume and Issue: 36(39), P. 395803 - 395803

Published: June 27, 2024

The magnetic properties of a circular graphene nanoribbon (carbon belt) in field parallel to its central axis is studied using tight-binding model. Orbital susceptibility calculated an analytical expression the energy eigenvalues as function flux density for any size, and temperature dependence considered. In absence electron hopping field, orbital diverges at absolute zero if chemical potential number atoms multiple four. As increases, magnitude decreases according power law, whose exponent depends on size. presence divergence near disappears, sign changes with transfer integral temperature.

Language: Английский

Nonalternant Nanographenes Containing N-Centered Cyclopenta[ef]heptalene and Aza[7]Helicene Units DOI
Shuhai Qiu, Abel Cárdenas Valdivia,

Weiwen Zhuang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(23), P. 16161 - 16172

Published: May 9, 2024

Introducing helical subunits into negatively curved π-systems has a significant effect on both the molecular geometry and photophysical properties; however, synthesis of these embedded with nonbenzenoid remains challenging due to high strain deriving from curvature helix. Here, we report family nonalternant nanographenes containing nitrogen (N)-doped cyclopenta[ef]heptalene unit. Among them, CPH-2 CPH-3 can be viewed as hybrids benzoannulated aza[7]helicene. The crystal structures revealed saddle for CPH-1, saddle-helix hybrid CPH-2, twist-helix CPH-3. Experimental measurements theoretical calculations indicate that moieties in CPHs undergo flexible conformational changes at room temperature, while aza[7]helicene subunit exhibits dramatically increased racemization energy barrier (78.2 kcal mol–1 143.2 CPH-3). combination lone electron pairs N-doped unit twisted helix fragments results rich photophysics distinctive fluorescence phosphorescence CPH-1 similar Both enantiopure display distinct circular dichroism (CD) signals UV–vis range. Notably, compared reported fully π-extended nanographenes, excellent chiroptical properties |gabs| value 1.0 × 10–2 |glum| 7.0 10–3; values are among highest nanographenes.

Language: Английский

Citations

15
Negatively Curved Octagon‐Incorporated Aza‐nanographene and its Assembly with Fullerenes DOI
Jun Liu, Juan Hong,

Zhenxing Liao

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(15)

Published: Feb. 12, 2024

Abstract A negatively curved aza‐nanographene (NG) containing two octagons was synthesized by a regioselective and stepwise cyclodehydrogenation procedure, in which double aza[7]helicene simultaneously formed as an intermediate. Their saddle‐shaped structures with negative curvature were unambiguously confirmed X‐ray crystallography, thereby enabling the exploration of structure–property relationship photophysical, electrochemical conformational studies. Moreover, assembly octagon‐embedded aza‐NG fullerenes probed fluorescence spectral titration, record‐high binding constants ( K =9.5×10 3 M −1 C 60 , =3.7×10 4 70 ) found among reported polycyclic aromatic compounds. The tight association further elucidated diffraction analysis their co‐crystal, showed formation 1 : complex substantial concave‐convex interactions.

Language: Английский

Citations

11
A High‐Yielding Active Template Click Reaction (AT−CuAAC) for the Synthesis of Mechanically Interlocked Nanohoops DOI
James H. May, Julia M. Fehr,

J. LORENZ

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(20)

Published: Feb. 22, 2024

Abstract Mechanically interlocked molecules (MIMs) represent an exciting yet underexplored area of research in the context carbon nanoscience. Recently, work from our group and others has shown that small nanotube fragments—[n]cycloparaphenylenes ([n]CPPs) related nanohoop macrocycles—may be integrated into mechanically architectures by leveraging supramolecular interactions, covalent tethers, or metal‐ion templates. Still, available synthetic methods are typically difficult low yielding, general allow for creation a wide variety these structures limited. Here we report efficient route to via active template Cu‐catalyzed azide‐alkyne cycloaddition (AT−CuAAC) reaction. With appropriate choice substituents, macrocyclic precursor 2,2′‐bipyridyl embedded [9]CPP (bipy[9]CPP) participates AT−CuAAC reaction provide [2]rotaxanes near‐quantitative yield, which can then converted fully π‐conjugated catenane structures. Through this approach, two nanohoop[2]catenanes synthesized consist bipy[9]CPP catenated with either Tz[10]CPP Tz[12]CPP (where Tz denotes 1,2,3‐triazole moiety replacing one phenylene ring [n]CPP backbone).

Language: Английский

Citations

11
Near-Infrared Perylenecarboximide Fluorophores for Live-Cell Super-Resolution Imaging DOI Creative Commons
Zehua Wu, Xingfu Zhu, Qiqi Yang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(11), P. 7135 - 7139

Published: March 5, 2024

Organic near-infrared (NIR) photoblinking fluorophores are highly desirable for live-cell super-resolution imaging based on single-molecule localization microscopy (SMLM). Herein we introduce a novel small chromophore, PMIP, through the fusion of perylenecarboximide with 2,2-dimetheylpyrimidine. PMIP exhibits an emission maximum at 732 nm high fluorescence quantum yield 60% in wavelength range 700–1000 and excellent without any additives. With resorcinol-functionalized (PMIP-OH), NIR SMLM lysosomes is demonstrated first time living mammalian cells under physiological conditions. Moreover, metabolically labeled nascent DNA site-specifically detected using azido-functionalized (PMIP-N3) via click chemistry, thereby enabling phosphate-buffered saline 9-fold improvement spatial resolution. These results indicate potential PMIP-based blinking biological applications SMLM.

Language: Английский

Citations

10
Helically Chiral π‐Expanded Azocines Through Regioselective Beckmann Rearrangement and Their Charged States DOI Creative Commons

Jan Borstelmann,

Lars Schneider,

Frank Röminger

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(29)

Published: May 8, 2024

Abstract We report a synthetic approach to π‐expanded [6]helicenes incorporating tropone and azocine units in combination with 5‐membered ring, which exhibit intriguing structural, electronic, chiroptical properties. The regioselective Beckmann rearrangement allows the isolation of helical scaffolds containing 8‐membered lactam, azocine, amine units. As shown by X‐ray crystallographic analysis, incorporation or leads highly distorted [6]helicene moieties, distinct packing motifs solid state. compounds promising optoelectronic properties considerable photoluminescence quantum yields tunable emission wavelengths depending on relative position nitrogen center within polycyclic framework. Separation enantiomers chiral high‐performance liquid chromatography (HPLC) allowed characterization their circular dichroism (CD) circularly polarized luminescence (CPL) spectroscopy. feature manifold redox chemistry, allowing for corresponding radical anions cations as well dications dianions, near‐infrared (NIR) absorption bands extending beyond 3000 nm. Detailed theoretical studies provided insights into aromaticity evolution upon reduction oxidation, suggesting that steric strain prevents unit from undergoing aromatization, while indene moiety dominates observed chemistry.

Language: Английский

Citations

7
Deep-Saddle-Shaped Nanographene Induced by Four Heptagons: Efficient Synthesis and Properties DOI

Boris Borrisov,

Giovanni M. Beneventi, Yubin Fu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 27, 2024

The construction of multiple heptagonal rings in nanographene is the key step for obtaining exotic carbon nanostructures with a negative curvature and intriguing properties. Herein, novel saddle-shaped (

Language: Английский

Citations

7
Chiral twisted molecular carbons: Synthesis, properties, and applications DOI Creative Commons

Yunqin Zhang,

Junjie Guan,

Leiquan Luo

et al.

Interdisciplinary materials, Journal Year: 2024, Volume and Issue: 3(4), P. 453 - 479

Published: May 11, 2024

Abstract In recent years, the precisely controlled synthesis of chiral twisted molecular carbons has emerged as a forefront topic in research carbon materials. Molecular refer to nanomaterials synthesized with precision at atomic level. Through rational design, rigid and stable structures can be synthesized. The exploration field is key fully understanding various configurations materials delving into relationship between structure design functionality. This review explores such nanographene, nanobelts, nanosheets, graphdiyne, etc. It emphasizes role photocyclization, Scholl reaction, Diels–Alder reactions achieving precise control discusses range innovative strategies. These strategies have led development structures, helical, propeller, Möbius strip configurations. introduction chirality, combined inherent exceptional optical properties nanocarbon materials, facilitated creation superior chiroptical performances. advancement driving applications fields optoelectronics optics.

Language: Английский

Citations

6
Toward three-dimensionally ordered nanoporous graphene materials: template synthesis, structure, and applications DOI Creative Commons
Masanori Yamamoto, Shunsuke Goto, Rui Tang

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 15(6), P. 1953 - 1965

Published: Dec. 26, 2023

Precise template synthesis will realize three-dimensionally ordered nanoporous graphenes (NPGs) with a spatially controlled seamless graphene structure and fewer edges. These structural features result in superelastic nature, high electrochemical stability, electrical conductivity, fast diffusion of gases ions at the same time. Such innovative 3D materials are conducive to solving energy-related issues for better future. To further improve attractive properties NPGs, we review its mechanism by chemical vapor deposition hydrocarbons, analysis structure, applications mechanical devices.

Language: Английский

Citations

11
Tethered Helical Ladder-Type Aromatic Lactams DOI
Huidong Xie, Zuo Xiao,

Yixiao Song

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(17), P. 11978 - 11990

Published: April 16, 2024

Tethered nonplanar aromatics (TNAs) make up an important class of aromatic compounds showing unique features. However, the knowledge on synthesis, structures, and properties TNAs remains insufficient. In this work, a new type TNAs, tethered lactams, is synthesized via Pd-catalyzed consecutive intramolecular direct arylations. These molecules possess helical ladder-type conjugated system to 13 fused rings. The overall yields ranged from 3.4 4.3%. largest 6L-Bu-C14, demonstrates guest-adaptive hosting capability for first time. When binding fullerene guests, cavity 6L-Bu-C14 became more circular better accommodate spherical molecules. host–guest interaction thoroughly studied by X-ray crystallography, theoretical calculations, fluorescence titration, nuclear magnetic resonance (NMR) titration experiments. shows stronger with C70 than C60 due convex–concave π–π interaction. P M enantiomers all lactams show distinct persistent chiroptical demonstrate potential chiral as circularly polarized luminescence (CPL) emitters.

Language: Английский

Citations

4
π-Extended Pyrenes: From Antiaromatic Buckybowl to Doubly Curved Nanocarbons with Gulf Architectures DOI Creative Commons
Binbin Liu,

Zhengxiong Jin,

Xinyue Liu

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

An antiaromatic buckybowl and two doubly curved nanocarbons by fusion of nonbenzenoid rings onto pyrene have been synthesized characterized.

Language: Английский

Citations

3