Engineering Small HOMO-LUMO Gaps in Polycyclic Aromatic Hydrocarbons with Topologically Protected States.

Topological phases in laterally confined low-dimensional nanographenes have emerged as versatile design tools that can imbue otherwise unremarkable materials with exotic band structures ranging from topological semiconductors and quantum dots to intrinsically metallic bands. The periodic boundary conditions that define the topology of a given lattice have thus far prevented the translation of this technology to the quasi-zero-dimensional (0D) domain of small molecular structures. Here, we describe the synthesis of a polycyclic aromatic hydrocarbon (PAH) featuring two localized zero modes (ZMs) formed by the topological junction interface between a trivial and nontrivial phase within a single molecule. First-principles density functional theory calculations predict a strong hybridization between adjacent ZMs that gives rise to an exceptionally small HOMO-LUMO gap. Scanning tunneling microscopy and spectroscopy corroborate the molecular structure of 9/7/9-double quantum dots and reveal an experimental quasiparticle gap of 0.16 eV, corresponding to a carbon-based small molecule long-wavelength infrared (LWIR) absorber.

Engineering Robust Metallic Zero-Mode States in Olympicene Graphene Nanoribbons.

Metallic graphene nanoribbons (GNRs) represent a critical component in the toolbox of low-dimensional functional materials technology serving as 1D interconnects capable of both electronic and quantum information transport. The structural constraints imposed by on-surface bottom-up GNR synthesis protocols along with the limited control over orientation and sequence of asymmetric monomer building blocks during the radical step-growth polymerization have plagued the design and assembly of metallic GNRs. Here, we report the regioregular synthesis of GNRs hosting robust metallic states by embedding a symmetric zero-mode (ZM) superlattice along the backbone of a GNR. Tight-binding electronic structure models predict a strong nearest-neighbor electron hopping interaction between adjacent ZM states, resulting in a dispersive metallic band. First-principles density functional theory-local density approximation calculations confirm this prediction, and the robust, metallic ZM band of olympicene GNRs is experimentally corroborated by scanning tunneling spectroscopy.

Spin splitting of dopant edge state in magnetic zigzag graphene nanoribbons.

Spin-ordered electronic states in hydrogen-terminated zigzag nanographene give rise to magnetic quantum phenomena1,2 that have sparked renewed interest in carbon-based spintronics3,4. Zigzag graphene nanoribbons (ZGNRs)-quasi one-dimensional semiconducting strips of graphene bounded by parallel zigzag edges-host intrinsic electronic edge states that are ferromagnetically ordered along the edges of the ribbon and antiferromagnetically coupled across its width1,2,5. Despite recent advances in the bottom-up synthesis of GNRs featuring symmetry protected topological phases6-8 and even metallic zero mode bands9, the unique magnetic edge structure of ZGNRs has long been obscured from direct observation by a strong hybridization of the zigzag edge states with the surface states of the underlying support10-15. Here, we present a general technique to thermodynamically stabilize and electronically decouple the highly reactive spin-polarized edge states by introducing a superlattice of substitutional N-atom dopants along the edges of a ZGNR. First-principles GW calculations and scanning tunnelling spectroscopy reveal a giant spin splitting of low-lying nitrogen lone-pair flat bands by an exchange field (~850 tesla) induced by the ferromagnetically ordered edge states of ZGNRs. Our findings directly corroborate the nature of the predicted emergent magnetic order in ZGNRs and provide a robust platform for their exploration and functional integration into nanoscale sensing and logic devices15-21.

Charge-Transfer Effects in Ligand Exchange Reactions of Au25 Monolayer-Protected Clusters.

Reported here are second-order rate constants of associative ligand exchanges of Au25L18 nanoparticles (L = phenylethanethiolate) of various charge states, measured by proton nuclear magnetic resonance at room temperature and below. Differences in second-order rate constants (M(-1) s(-1)) of ligand exchange (positive clusters ∼1.9 × 10(-5) versus negative ones ∼1.2 × 10(-4)) show that electron depletion retards ligand exchange. The ordering of rate constants between the ligands benzeneselenol > 4-bromobenzene thiol > benzenethiol reveals that exchange is accelerated by higher acidity and/or electron donation capability of the incoming ligand. Together, these observations indicate that partial charge transfer occurs between the nanoparticle and ligand during the exchange and that this is a rate-determining effect in the process.

Temperature dependence of solid-state electron exchanges of mixed-valent ferrocenated Au monolayer-protected clusters.

Electron transfers (ETs) in mixed-valent ferrocene/ferrocenium materials are ordinarily facile. In contrast, the presence of ~1:1 mixed-valent ferrocenated thiolates in the organothiolate ligand shells of <2 nm diameter Au225, Au144, and Au25 monolayer-protected clusters (MPCs) exerts a retarding effect on ET between them at and below room temperature. Near room temperature, in dry samples, bimolecular rate constants for ET between organothiolate-ligated MPCs are diminished by the addition of ferrocenated ligands to their ligand shells. At lower temperatures (down to ~77 K), the thermally activated (Arrhenius) ET process dissipates, and the ET rates become temperature-independent. Among the Au225, Au144, and Au25 MPCs, the temperature-independent ET rates fall in the same order as at ambient temperatures: Au225 > Au144 > Au25. The MPC ET activation energy barriers are little changed by the presence of ferrocenated ligands and are primarily determined by the Au nanoparticle core size.