The atomically precise control over the size, shape and structure of nanographenes (NGs) or the introduction of heteroatom dopants into their sp -carbon lattice confer them valuable electronic, optical and magnetic properties. Herein, we report on the design and synthesis of a hexabenzocoronene derivative embedded with graphitic nitrogen in its honeycomb lattice, achieved via on-surface assisted cyclodehydrogenation on the Au(111) surface. Combined scanning tunnelling microscopy/spectroscopy and non-contact atomic force microscopy investigations unveil the chemical and electronic structures of the obtained dicationic NG. Kelvin probe force microscopy measurements reveal a considerable variation of the local contact potential difference toward lower values with respect to the gold surface, indicative of its positive net charge. Altogether, we introduce the concept of cationic nitrogen doping of NGs on surfaces, opening new avenues for the design of novel carbon nanostructures.
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http://dx.doi.org/10.1002/anie.202111863 | DOI Listing |
Nat Commun
January 2025
Faculty of Mathematics and Physics, University of Ljubljana, Ljubljana, Slovenia.
We present an efficient strategy for on-surface engineering of organic metal-free supramolecular complexes with long-term spin protection. By vacuum deposition of azafullerene (CN) monomers on a pre-deposited template layer of [10]cycloparaphenylene ([10]CPP) nanohoops on Au(111) surface we exploit the molecular shape matching between the CN and [10]CPP for the azafullerene encapsulation with nanohoops in a guest-host complexation geometry. CN⊂[10]CPP supramolecular complexes self-assemble into an extended two-dimensional hexagonal lattice yielding a high density network of stable spin-1/2 radicals.
View Article and Find Full Text PDFChemistry
December 2024
University of Trieste, Department of Chemical and Pharmaceutical Sciences, Via Licio Giorgieri, 1, 34127, Trieste, ITALY.
In this work, we elucidate the electronic charge redistributions that occur within the cyanuric acid (CA) and melamine (M) molecules upon formation of the triple H-bond between the imide group of CA and the diaminopyridine group of M. To achieve this, we investigated 2D H-bonded assemblies of M, CA and CA*M grown on the Au(111) surface, using X-ray photoemission (XPS) and near edge X-ray absorption fine structure (NEXAFS) spectroscopies. Compared to the homomolecular networks, the spectra of the mixed sample reveal core level shifts in opposite directions for CA and M, indicating a nearly complementary charge accumulation on the CA molecule and a charge depletion on the M molecule.
View Article and Find Full Text PDFLangmuir
December 2024
Lehrstuhl für Physikalische Chemie 2, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen, Germany.
We studied the adsorption and thermal behavior of the nitrile-functionalized ionic liquid (IL) [CCNCIm][TfN] on Au(111) and Pt(111) between 150 and 600 K. Ultrathin films were prepared at 150 K by physical vapor deposition (PVD) and were characterized by angle resolved X-ray photoelectron spectroscopy (ARXPS). At 150 K, the IL adsorbs intact with a similar orientation on both surfaces: In the first layer, the so-called wetting layer, the cation lies flat on the surface and the anion is bound in -configuration with the SO groups toward the surface and the CF groups away from the surface.
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
Department of Applied Physics, Aalto University, Helsinki 02150, Finland.
Scanning probe microscopy (SPM) techniques have shown great potential in fabricating nanoscale structures endowed with exotic quantum properties achieved through various manipulations of atoms and molecules. However, precise control requires extensive domain knowledge, which is not necessarily transferable to new systems and cannot be readily extended to large-scale operations. Therefore, efficient and autonomous SPM techniques are needed to learn optimal strategies for new systems, in particular for the challenge of controlling chemical reactions and hence offering a route to precise atomic and molecular construction.
View Article and Find Full Text PDFACS Nano
December 2024
Department of Chemistry and Center of Super-Diamond & Advanced Films, City University of Hong Kong, Kowloon, Hong Kong 999077, China.
The large-scale preparation of two-dimensional (2D) materials is pivotal in unlocking their extensive potential for next-generation semiconductor device applications. Wafer-scale single crystals of a high-symmetry 2D material (e.g.
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