Topological design and synthesis of high-spin aza-triangulenes without Jahn-Teller distortions

The atomic doping of open-shell nanographenes enables the precise tuning of their electronic and magnetic state, which is crucial for their promising potential applications in optoelectronics and spintronics. Among this intriguing class of molecules, triangulenes stand out with their size-dependent electronic properties and spin states, which can also be influenced by the presence of dopant atoms and functional groups. However, the occurrence of Jahn-Teller distortions in such systems can have a crucial impact on their total spin and requires further theoretical and experimental investigation. In this study, we examine the nitrogen-doped aza-triangulene series via a combination of density functional theory and on-surface synthesis. We identify a general trend in the calculated spin states of aza-[n]triangulenes of various sizes, separating them into two symmetry classes, one of which features molecules that are predicted to undergo Jahn-Teller distortions that reduce their symmetry and thus their total spin. We link this behavior to the location of the central nitrogen atom relative to the two underlying carbon sublattices of the molecules. Consequently, our findings reveal that centrally-doped aza-triangulenes have one less radical than their undoped counterparts, irrespective of their predicted symmetry. We follow this by demonstrating the on-surface synthesis of {\pi}-extended aza-[5]triangulene, a large member of the higher symmetry class without Jahn-Teller distortions, via a simple one-step annealing process on Cu(111) and Au(111). Using scanning probe microscopy and spectroscopy combined with theoretical calculations, we prove that the molecule is positively charged on the Au(111) substrate, with a high-spin quintet state of S = 2, the same total spin as undoped neutral [5]triangulene.Comment: Main paper 18 pages, 5 figures. Removed hyphen from author name, addded funding information for one autho

新規炭素ナノリボンの表面合成に関する研究

京都大学0048新制・課程博士博士(エネルギー科学)甲第20728号エネ博第356号新制||エネ||70(附属図書館)京都大学大学院エネルギー科学研究科エネルギー基礎科学専攻(主査)教授 坂口 浩司, 教授 萩原 理加, 教授 佐川 尚学位規則第4条第1項該当Doctor of Energy ScienceKyoto UniversityDFA

Substrate induced strain for on-surface transformation and synthesis

10.1039/d0nr01270jNanoscale12147500-750

On-surface Synthesis of [7]triangulene Quantum Ring via Antidot Engineering

The ability to engineer geometrically well-defined antidots in large triangulene homologues allows for creating an entire family of triangulene quantum ring (TQR) structures with tunable high-spin ground state and magnetic ordering, crucial for next-generation 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 coronene-like antidot in the molecular centre. 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 (� = 3) on Au(111). This work demonstrates a new route for the design of high-spin graphene quantum rings as the key components for future quantum devices

Tailoring Long-Range Superlattice Chirality in the Molecular Selfassemblies via Weak Fluorine-Mediated Interactions

Controllable fabrication of the enantiospecific molecular superlattices is a matter of imminent scientific and technological interest. Herein, we demonstrate that long-range superlattice chirality in molecular self-assemblies can be tailored by tuning the interplay of weak intermolecular non-covalent interactions. Different chiral recognition patterns are achieved in the two molecular self-assemblies comprised by two molecular enantiomers with identical steric conformations, derived from the hexaphenylbenzene – the smallest star-shaped polyphenylene. By means of high-resolution scanning tunneling microscopy measurements, we demonstrate that functionalization of star-shaped polyphenylene with fluorine (F) atoms leads to the formation of molecular self-assemblies with the distinct long-range chiral recognition patterns. We employed the density functional theory calculations to quantify F-mediated lone pair F ···π, C-H··· F, F···F interactions attributed to the tunable enantiospecific molecular self-organizations. Our findings underpin a viable route to tailor long-range chiral recognition patterns in supramolecular assemblies by engineering the weak non-covalent intermolecular interactions

Ultra-high Yield On-surface Synthesis and Assembly of Circumcoronene into Chiral Electronic Kagome-honeycomb Lattice

On-surface synthesis has revealed remarkable potential in the fabrication of a plethora of elusive nanographenes with tailored structural, electronic and magnetic properties unattainable by conventional wet-chemistry synthesis. Unfortunately, surface-assisted synthesis often involves multiple-step cascade reactions with competing pathways, leading to the formation of a diversity of products with limited yield, which reduces its feasibility towards the large-scale production for future technological applications. Here, we devise a new on-surface synthetic strategy for the ultra-high yield synthesis of a hexagonal nanographene with six zigzag edges, namely circumcoronene on Cu(111) via surfaceassisted intramolecular dehydrogenation of the rationally-designed precursor molecule, followed by methyl radical-radical coupling and aromatization. An elegant electrostatic interaction between circumcoronene and Cu(111) drives their self-organization into an extended superlattice, as revealed by bond-resolved low-temperature scanning probe microscopy and spectroscopy 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 (2D) electron gas in Cu(111) surface into 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 novel 2D superlattices with possible nontrivial electronic properties towards their future technological applications

Highly-Entangled Polyradical Nanographene with Coexisting Strong Correlation and Topological Frustration

Open-shell benzenoid polycyclic aromatic hydrocarbons, known as magnetic nanographenes, exhibit unconventional π-magnetism arising from topological frustration or strong electronic-electron interaction. Imprinting multiple strongly entangled spins into polyradical nanographenes creates a major paradigm shift in realizing non-trivial collective quantum behaviors and exotic quantum phases in organic quantum materials. However, conventional design approaches are limited by a single magnetic origin, which can restrict the number of correlated spins or the type of magnetic ordering in open-shell nanographenes. Here, we present a novel design strategy combing topological frustration and electron-electron interactions to fabricate the largest fully-fused open-shell nanographene reported to date, a 'butterfly'-shaped tetraradical on Au(111). We employed bond-resolved scanning tunneling microscopy and spin excitation spectroscopy to unambiguously resolve the molecular backbone and reveal the strongly correlated open-shell character, respectively. This nanographene contains four unpaired electrons with both ferromagnetic and anti-ferromagnetic interactions, harboring a many-body singlet ground state and strong multi-spin entanglement, which can be well described by many-body calculations. Furthermore, we demonstrate that the nickelocene magnetic probe can sense highly-correlated spin states in nanographene. The ability to imprint and characterize many-body strongly correlated spins in polyradical nanographenes not only presents exciting opportunities for realizing non-trivial quantum magnetism and phases in organic materials but also paves the way toward high-density ultrafast spintronic devices and quantum information technologies

Visualizing designer quantum states in stable macrocycle quantum corrals

10.1038/s41467-021-26198-8Nature Communications121589