Quantum Phase Transition in Magnetic Nanographenes on a Lead Superconductor.

Quantum spins, also known as spin operators that preserve SU(2) symmetry, lack a specific orientation in space and are hypothesized to display unique interactions with superconductivity. However, spin-orbit coupling and crystal field typically cause a significant magnetic anisotropy in d/f shell spins on surfaces. Here, we fabricate atomically precise S = 1/2 magnetic nanographenes on Pb(111) through engineering sublattice imbalance in the graphene honeycomb lattice. Through tuning the magnetic exchange strength between the unpaired spin and Cooper pairs, a quantum phase transition from the singlet to the doublet state has been observed, consistent with the quantum spin models. From our calculations, the particle-hole asymmetry is induced by the Coulomb scattering potential and gives a transition point about kBTk ≈ 1.6Δ. Our work demonstrates that delocalized π electron magnetism hosts highly tunable magnetic bound states, which can be further developed to study the Majorana bound states and other rich quantum phases of low-dimensional quantum spins on superconductors.

Synthesis of Dendronized Polymers on the Au(111) Surface.

Dendronized polymers (DPs) consist of a linear polymeric backbone with dendritic side chains. Fine-tuning of the functional groups in the side chains enriches the structural versatility of the DPs and imparts a variety of novel physical properties. Herein, the first on-surface synthesis of DPs is achieved via the postfunctionalization of polymers on Au(111), in which the surface-confinement-induced planar conformation and chiral configurations were unambiguously characterized. While the dendronized monomer was synthesized in situ on Au(111), the subsequent polymerization afforded only short, cross-linked DP chains owing to multiple side reactions. The postfunctionalization approach selectively produced brominated polyphenylene backbone moieties by the deiodination polymerization of 4-bromo-4″-iodo-5'-(4-iodophenyl)-1,1':3',1″-terphenyl on Au(111), which smoothly underwent divergent cross-coupling reactions with two different isocyanides to form two types of DPs as individual long chains.

On-Surface Synthesis of [3]Radialenes via [1+1+1] Cycloaddition.

[3]Radialenes are the smallest carbocyclic structures with unusual topologies and cross-conjugated π-electronic structures. Here, we report a novel [1+1+1] cycloaddition reaction for the synthesis of aza[3]radialenes on the Ag(111) surface, where the steric hindrance of the chlorine substituents guides the selective and orientational assembling of the isocyanide precursors. By combining scanning tunneling microscopy, non-contact atomic force microscopy, and time-of-flight secondary ion mass spectrometry, we determined the atomic structure of the produced aza[3]radialenes. Furthermore, two reaction pathways including synergistic and stepwise are proposed based on density functional theory calculations, which reveal the role of the chlorine substituents in the activation of the isocyano groups via electrostatic interaction.