arXiv subjects

Li-Xia Kang

Publications and source records attributed to Li-Xia Kang.

3 recordsLinked to original sources

arXiv2026

Steering Selective Formation and 2D Crystallization of [4]Radialenes on Au(111) via [1+1+1+1] Cycloaddition of Isocyanides and Enantioselective Molecular Recognition

Conjugated carbon rings are fundamental skeletons of organic functional materials, and their selective formation is of paramount importance in molecular materials engineering. However, steering the formation and 2D crystallization of conjugated carbon rings on the surface with high chemo- and stereoselectivities remains a great challenge. Here, we report a highly chemoselective [1+1+1+1] cycloaddition of isocyanides on the Au(111) surface, which affords the stereospecific tetraaza[4]radialene products and further enables their long-range-ordered 2D crystallization via enantioselective molecular recognition. Using the progressive annealing method, we found that at room temperature, isocyanides undergo a coordination reaction with Au adatoms to form two-fold symmetric isocyanide-Au-isocyanide complexes. In contrast, gradually increasing the annealing temperature induces the transformation of these complexes and subsequent covalent polymerization, leading to the selective generation of tetraaza[4]radialenes with homotactic configurations. The tetraaza[4]radialenes further assemble into 2D homochiral molecular crystals through enantioselective molecular recognition driven by multiple C-H -- Cl hydrogen-bonding interactions. By combining scanning tunneling microscopy/spectroscopy and non-contact atomic force microscopy, we determined the atomic structure and molecular orbitals of tetraaza[4]radialene, confirming that its four-membered ring adopts a planar geometry with a localized lowest unoccupied molecular orbital. Density functional theory calculations suggest that the [1+1+1+1] cycloaddition process involves stepwise formation of C-C bonds and its high selectivity arises from the spatial steric hindrance. Our findings provide new insights into the selective formation of conjugated rings on surfaces and have implications for engineering 2D homochiral molecular crystallization.

cond-mat.mtrl-sci↗

arXiv2026

Synthesis of single-layered fluorographdiyne nanosheets via selective on-surface 2D covalent polymerization

Two-dimensional conjugated polymers (2DCPs) are significant macromolecular materials with intriguing and tunable physicochemical properties that depend on their geometries. Graphdiyne and its derivatives are exemplary 2DCPs featuring sp-sp2 hybridized skeletons. However, achieving single-layered, large-domain/regular graphdiyne and its derivatives on surfaces remains a formidable challenge due to the lack of selective 2D covalent polymerization methods. Here, we report a selective on-surface 2D covalent polymerization method via the combination of cobalt catalysis and coronene templating, achieving the synthesis of single-layered fluorographdiyne nanosheets up to 60*60 nm2 on Au(111) surface. Using scanning probe techniques, we visualize the sequential polymerization process and characterize cobalt-activated coupling intermediates at the atomic level. Experimental and theoretical analyses suggest that strong d-{\pi} coupling between cobalt and alkynyl transforms a robust Csp-Au bond into a weaker Csp2-Au bond, thereby facilitating the demetallization C-C coupling. Besides, the templating effect of coronene suppresses kinetically trapped defects and improves the selectivity of hexagonal-ring formation in the complex 2D covalent polymerization process.

cond-mat.mtrl-sci↗

arXiv2025

Engineering Graphene Nanoribbons via Periodically Embedding Oxygen Atoms

Heteroatom doping is an important method for engineering graphene nanoribbons (GNRs) because of its ability to modify electronic properties by introducing extra electrons or vacancies. However, precisely integrating oxygen atoms into the lattice of GNRs is unexplored, and the resulting electronic properties remain elusive. Here, we achieve the precise embedding of oxygen atoms into the lattice of GNRs via in situ formation of pyrans, synthesizing two types of oxygen-doped GNRs (O-doped chevron-GNR and O-doped chiral (2,1)-GNR). Using scanning tunneling microscopy, non-contact atomic force microscopy, and density functional theory calculations, the atomic structures and electronic properties of O-doped GNRs are determined, demonstrating that both GNRs are direct bandgap semiconductors with different sensitivities to oxygen dopants. Oxygen dopants have a minor impact on the bandgap of chevron-GNR but a significant effect on the bandgap of chiral (2,1)-GNR, which is attributed to the difference in density of states near the Fermi level between substituted intrinsic carbon atoms and their pristine counterparts. Compared with the pristine chiral (2,1)-GNR, the band structure of O-doped chiral (2,1)-GNR exhibits unexpected band edges transition, which is ascribed to sp2-hybridized oxygen atoms which introduces additional electrons to the conduction band of chiral (2,1)-GNR, leading to the upward shift of Fermi surface.

cond-mat.mtrl-sci↗