The ability to precisely engineer the doping of sub-nanometer bimetallic clusters offers exciting opportunities for tailoring their catalytic performance with atomic accuracy. However, the fabrication of singly dispersed bimetallic cluster catalysts with atomic-level control of dopants has been a long-standing challenge. Herein, we report a strategy for the controllable synthesis of a precisely doped single cluster catalyst consisting of partially ligandenveloped Au 4 Pt 2 clusters supported on defective graphene. This creates a bimetal single cluster catalyst (Au 4 Pt 2 /G) with exceptional activity for electrochemical nitrogen (N 2) reduction. Our mechanistic study reveals that each N 2 molecule is activated in the confined region between cluster and graphene. The heteroatom dopant plays an indispensable role in the activation of N 2 via an enhanced back donation of electrons to the N 2 LUMO. Moreover, besides the heteroatom Pt, the catalytic performance of single cluster catalyst can be further tuned by using Pd in place of Pt as the dopant.

The ability to engineer geometrically well-defined antidots in large triangulene homologues allows for creating an entire family of triangulene quantum rings (TQRs) with tunable high-spin ground state, crucial for nextgeneration molecular spintronic devices. Herein, we report the synthesis of an open-shell [7]triangulene quantum ring ([7]TQR) molecule on Au(111) through the surface-assisted cyclodehydrogenation of a rationally designed kekulene derivative. Bond-resolved scanning tunneling microscopy (BR-STM) unambiguously imaged the molecular backbone of a single [7]TQR with a triangular zigzag edge topology, which can be viewed as [7]triangulene decorated with a coronenelike antidot in the center. Additionally, dI/dV mapping reveals that both inner and outer zigzag edges contribute to the edge-localized and spin-polarized electronic states of [7]TQR. Both experimental results and spin-polarized density functional theory calculations indicate that [7]TQR retains its open-shell septuple ground state (S = 3) on Au(111). This work demonstrates a new route for the design of high-spin graphene quantum rings for future quantum devices.

On-surface synthesis has revealed remarkable potential in the fabrication of atomically precise nanographenes. However, surface-assisted synthesis often involves multiple-step cascade reactions with competing pathways, leading to a limited yield of target nanographene products. Here, we devise a strategy for the ultrahigh-yield synthesis of circumcoronene molecules on Cu(111) via surface-assisted intramolecular dehydrogenation of the rationally designed precursor, followed by methyl radical-radical coupling and aromatization. An elegant electrostatic interaction between circumcoronenes and metallic surface drives their self-organization into an extended superlattice, as revealed by bond-resolved scanning probe microscopy measurements. Density functional theory and tight-binding calculations reveal that unique hexagonal zigzag topology of circumcoronenes, along with their periodic electrostatic landscape, confines two-dimensional electron gas in Cu(111) into a chiral electronic Kagome-honeycomb lattice with two emergent electronic flat bands. Our findings open up a new route for the high-yield fabrication of elusive nanographenes with zigzag topologies and their superlattices with possible nontrivial electronic properties.

Ferromagnetism and superconductivity are two antagonistic phenomena since ferromagnetic exchange fields tend to destroy singlet Cooper pairs. Reconciliation of these two competing phases has been achieved in vertically stacked heterostructures where these two orders are confined in different layers. However, controllable integration of these two phases in one atomic layer is a longstanding challenge. Here, an interlayer‐space‐confined chemical design (ICCD) is reported for the synthesis of dilute single‐atom‐doped TaS2 molecular superlattice, whereby ferromagnetism is observed in the superconducting TaS2 layers. The intercalation of 2H‐TaS2 crystal with bulky organic ammonium molecule expands its van der Waals gap for single‐atom doping via co‐intercalated cobalt ions, resulting in the formation of quasi‐monolayer Co‐doped TaS2 superlattices. Isolated Co atoms are decorated in the basal plane of the TaS2 via substituting the Ta atom or anchoring at a hollow site, wherein the orbital‐selected p–d hybridization between Co and neighboring Ta and S atoms induces local magnetic moments with strong ferromagnetic coupling. This ICCD approach can be applied to various metal ions, enabling the synthesis of a series of crystal‐size TaS2 molecular superlattices.

Organic radicals consisting of light elements exhibit a low spin–orbit coupling and weak hyperfine interactions with a long spin coherence length, which are crucial for future applications in molecular spintronics. However, the synthesis and characterization of these organic radicals have been a formidable challenge due to their chemical instability arising from unpaired electrons. Here, we report a direct imaging of the surface chemical transformation of an organic monoradical synthesized via the monodehydrogenation of a chemically designed precursor. Bond-resolved scanning tunneling microscopy unambiguously resolves various products formed through a complex structural dissociation and rearrangement of organic monoradicals. Density functional theory calculations reveal detailed reaction pathways from the monoradical to different cyclized products. Our study provides unprecedented insights into complex surface reaction mechanisms of organic radical reactions at the single molecule level, which may guide the design of stable organic radicals for future quantum technology applications.