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Triangulene, one unique class of zigzag-edged triangular graphene molecules, has attracted tremendous research interest. In this work, as an ultimate phase of the Mott insulator, we present the realization of the atomic-limit Mott insulator in experimentally synthesized [4]triangulene frameworks ([4]-TGFs) from first-principles calculations. The frontier molecular orbitals of the nonmagnetic [4]triangulene consist of three coupled corner modes. After the isolated [4]triangulene is assembled into [4]-TGF, one special enantiomorphic flat band is created through the coupling of these corner modes, which is identified to be a second-order topological insulator with half-filled topological corner states at the Fermi level. Moreover, [4]-TGF prefers an antiferromagnetic ground state under Hubbard interactions, which further splits these metallic zero-energy states into an atomic-limit Mott insulator with spin-polarized corners. Since the fractional filling of topological corner states is a smoking-gun signature of higher-order topology, our results demonstrate a universal approach to explore the atomic-limit Mott insulators in higher-order topological materials.
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On-surface synthesis has paved the way toward the fabrication and characterization of conjugated carbon-based molecular materials that exhibit π-magnetism such as triangulenes. Aza-triangulene, a nitrogen-substituted derivative, was recently shown to display rich on-surface chemistry, offering an ideal platform to investigate structure-property relations regarding spin-selective charge transfer and magnetic fingerprints. Herein, we study electronic changes upon fusion of single molecules into larger dimeric derivatives. We show that the closed-shell structure of aza-triangulene on Ag(111) leads to closed-shell dimers covalently coupled through sterically accessible carbon atoms. Meanwhile, its open-shell structure on Au(111) leads to coupling via atoms displaying a high spin density, resulting in symmetric or asymmetric products. Interestingly, whereas all dimers on Au(111) exhibit similar charge transfer properties, only asymmetric ones show magnetic fingerprints due to spin-selective charge transfer. These results expose clear relationships among molecular symmetry, charge transfer, and spin states of π-conjugated carbon-based nanostructures.
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Triangulenes as neutral radicals are becoming promising candidates for future applications such as spintronics and quantum technologies. To extend the potential of the advanced materials, it is of importance to control their electronic and magnetic properties by multiple graphitic nitrogen doping. Here, we synthesize triaza[5]triangulene on Au(111) by cyclodehydrogenation, and its derivatives by cleaving C-N bonds. Bond-resolved scanning tunneling microscopy and scanning tunneling spectroscopy provided detailed structural information and evidence for open-shell singlet ground state. The antiferromagnetic arrangement of the spins in positively doped triaza[5]triangulene was further confirmed by density function theory calculations. The key aspect of triangulenes with multiple graphitic nitrogen is the extra pz electrons composing the π orbitals, favoring charge transfer to the substrate and changing their low-energy excitations. Our findings pave the way for the exploration of exotic low-dimensional quantum phases of matter in heteroatom doped organic systems.
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In this work, we theoretically investigate the linear and nonlinear optical absorption properties of open triangulene spin chains and cyclic triangulene spin chains in relation to their lengths and shapes. The physical mechanism of local excitation within the triangular alkene unit and the weak charge transfer between the units are discussed. The uniformly distributed electrostatic potential allows the system to have a small permanent dipole moment that blocks the electronic transition in the light excitation such that the electronic transition can only be carried out between adjacent carbon atoms. The one-photon absorption (OPA) spectra and two-photon absorption (TPA) spectra are red-shifted with the addition of triangulene units compared to N = 3TSCs (triangulene spin chains, TSCs). Here, TPA is mainly caused by the first step of the transition. The length of the spin chain has a significant adjustment effect on the photon cross-section. TSCs of different lengths and shapes can control chirality by adjusting the distribution of the electric dipole moment and transition magnetic dipole moment. These analyses reveal the photophysical properties of triangulene and provide a theoretical basis for studying the photophysical properties of triangulene and its derivatives.
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A kinetically-stabilized nitrogen-doped triangulene cation derivative has been synthesized and isolated as the stable diradical with a triplet ground state that exhibits near-infrared emission. As was the case for a triangulene derivative we previously synthesized, the triplet ground state with a large singlet-triplet energy gap was experimentally confirmed by magnetic measurements. In contrast to the triangulene derivative, the nitrogen-doped triangulene cation derivative is highly stable even in solution under air and exhibits near-infrared absorption and emission because the alternancy symmetry of triangulene is broken by the nitrogen cation. Breaking the alternancy symmetry of triplet alternant hydrocarbon diradicals by a nitrogen cation would therefore be an effective strategy to create stable diradicals possessing magnetic properties similar to the parent hydrocarbons but with different electrochemical and photophysical properties.
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Triangulenes are a class of open-shell triangular graphene flakes with total spin increasing with their size. In the last years, on-surface-synthesis strategies have permitted fabricating and engineering triangulenes of various sizes and structures with atomic precision. However, direct proof of the increasing total spin with their size remains elusive. In this work, we report the combined in-solution and on-surface synthesis of a large nitrogen-doped triangulene (aza-[5]-triangulene) on a Au(111) surface, and the detection of its high-spin ground state. Bond-resolved scanning tunneling microscopy images uncovered radical states distributed along the zigzag edges, which were detected as weak zero-bias resonances in scanning tunneling spectra. These spectral features reveal the partial Kondo screening of a high-spin state. Through a combination of several simulation tools, we find that the observed distribution of radical states is explained by a quintet ground state (S=2), instead of the quartet state (S=3/2) expected for the neutral species. This confirms that electron transfer to the metal substrate raises the spin of the ground state. We further provide a qualitative description of the change of (anti)aromaticity introduced by N-substitution, and its role in the charge stabilization on a surface, resulting in an S=2 aza-triangulene on Au(111).
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Large graphene-like molecules with four zigzag edges are ideal gain medium materials for organic near-infrared (NIR) lasers. However, synthesizing them becomes increasingly challenging as the molecular size increases. In this study, we introduce a new intramolecular radical-radical coupling approach and successfully synthesize two fused triangulene dimers (1 a/1 b) efficiently. X-ray crystallographic analysis of 1 a indicates that there is no intermolecular π-π stacking in the solid state. When the more soluble derivative 1 b is dispersed in polystyrene thin films, amplified spontaneous emission in the NIR region is observed. Using 1 b as the active gain material, we fabricate solution-processed distributed feedback lasers that exhibit a narrow emission linewidth at around 790â nm. The laser devices also exhibit low thresholds with high photostability. Our study provides a new synthetic strategy for extended nanographenes, which have diverse applications in electronics and photonics.
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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 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 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.
RESUMO
Synthesis of triangulene and its derivatives is challenging due to their intrinsic high spin nature. Herein, we report solution-phase synthesis and isolation of a nitrogen-doped triangulene (i.e., aza-triangulene) (NT) and its cation (NT+ ) in single-crystal form. Notably, the cation NT+ can be regarded as an isoelectronic structure of the corresponding all-carbon triangulene. Both NT and NT+ show reasonable stability due to kinetic blocking by bulky and electron-withdrawing aryl substituents, and intramolecular donor-acceptor interaction. Bond length analysis, magnetic measurements and theoretical calculations reveal that the neutral NT has a doublet ground state with a zwitterionic character, while the cation NT+ exhibits a triplet ground state with a singlet-triplet energy gap of +0.84â kcal mol-1 . This study provides a rational strategy to access high-spin systems by heteroatom doping of pure π-conjugated polycyclic hydrocarbons.
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Triangulenes have attracted enormous interest in organic chemistry and materials science, but suffer from their high instability towards oxygen. Embedding heteroatoms into triangulenes provides a new class of ambient stable materials for various applications. However, [3]heterotriangulenes have dominated the chemistry of heteroatom-doped triangulenes, while their higher homologues have been rarely explored. In this work, we synthesize a new [4]heterotriangulene with three oxygen-boron-oxygen (OBO) segments incorporated into the zigzag edges. The planar geometry of the OBO-doped [4]triangulene is demonstrated by single-crystal X-ray diffraction. Self-assembly on metal surfaces reveals substrate-dependent nanostructures, leading to different long-range ordered 2D patterns on Ag and Cu substrates with negligible defects.
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Triangulene nanographenes are open-shell molecules with predicted high spin state due to the frustration of their conjugated network. Their long-sought synthesis became recently possible over a metal surface. Here, we present a macrocycle formed by six [3]triangulenes, which was obtained by combining the solution synthesis of a dimethylphenyl-anthracene cyclic hexamer and the on-surface cyclodehydrogenation of this precursor over a gold substrate. The resulting triangulene nanostar exhibits a collective spin state generated by the interaction of its 12 unpaired π-electrons along the conjugated lattice, corresponding to the antiferromagnetic ordering of six S=1 sites (one per triangulene unit). Inelastic electron tunneling spectroscopy resolved three spin excitations connecting the singlet ground state with triplet states. The nanostar behaves close to predictions from the Heisenberg model of an S=1 spin ring, representing a unique system to test collective spin modes in cyclic systems.
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Cationic BN-embedded polycyclic aromatic hydrocarbons (BN-PAH+ s) were synthesized from a nitrogen-containing macrocycle via pyridine-directed tandem C-H borylation. Incorporating BN into PAH+ resulted in a remarkable hypsochromic shift due to an increase in the LUMO energy and the symmetry changes of the HOMO and LUMO. Electrophilic substitution or anion exchange of BN-PAH+ possessing tetrabromoborate as a counter anion (BN+ [BBr4 - ]) afforded air-stable BN-PAH/PAH+ s. Of these, BN+ [TfO- ] allowed reversible two-electron reduction and the formation of two-dimensional brickwork-type π-electronic ion pair with 1,2,3,4,5-pentacyanocyclopentadienyl anion, demonstrating the potential application of BN-PAH+ as electronic materials.
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Triangulenes are of current interest for potential applications in molecular electronics. We describe here a three step synthesis of the 4,8,12-trihydro[3]triangulenium cation by cascade cyclization of a tetra-benzyl alcohol precursor in triflic acid solution. This stable carbocation is easily observed by NMR and optical spectroscopy and is highly fluorescent. Quenching of the cation into basic solutions or by hydride transfer from triethylsilane provides access to stable dihydro and tetrahydro[3]triangulenes. These neutral species interconvert with cations in a complex series of proton and hydride transfers. This route provides several important [3]triangulene precursors. Preliminary experiments designed to generate [3]triangulene in the solution phase provide evidence for its formation and rapid oligomerization.
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We show that the diradicaloid triangulene, a graphene nano-flake molecule, can aggregate in a variety of dimerization modes. We found by density functional theory modeling a number of triangulene dimers including six doubly bonded σ-dimers in addition to the previously reported six pancake bonded π-dimer isomers. The σ-dimers display a wide range of stabilities: the interaction energy of the most stable σ-dimer is -25.17â kcal mol-1 . Besides the doubly bonded σ-dimers with closed shell ground states, we also found an open-shell singly σ-bonded diradicaloid dimer. We found an interesting isomerization route between a doubly bonded σ-dimer, a singly bonded σ-dimer with a low-lying triplet state and two π-bonded dimers with low-lying quintet states. Derivatives of triangulene, trioxo-triangulenes (TOTs) have been previously characterized experimentally. Here, we show the reasons why so far only the π-dimer but not the σ-dimer was experimentally observed for all TOTs.
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Relative to conventional wet-chemical synthesis techniques, on-surface synthesis of organic networks in ultrahigh vacuum has few control parameters. The molecular deposition rate and substrate temperature are typically the only synthesis variables to be adjusted dynamically. Here we demonstrate that reducing conditions in the vacuum environment can be created and controlled without dedicated sourcesârelying only on backfilled hydrogen gas and ion gauge filamentsâand can dramatically influence the Ullmann-like on-surface reaction used for synthesizing two-dimensional covalent organic frameworks (2D COFs). Using tribromo dimethylmethylene-bridged triphenylamine ((Br3)DTPA) as monomer precursors, we find that atomic hydrogen (Hâ¢) blocks aryl-aryl bond formation to such an extent that we suspect this reaction may be a factor in limiting the ultimate size of 2D COFs created through on-surface synthesis. Conversely, we show that control of the relative monomer and hydrogen fluxes can be used to produce large self-assembled islands of monomers, dimers, or macrocycle hexamers, which are of interest in their own right. On-surface synthesis of oligomers, from a single precursor, circumvents potential challenges with their protracted wet-chemical synthesis and with multiple deposition sources. Using scanning tunneling microscopy and spectroscopy (STM/STS), we show that changes in the electronic states through this oligomer sequence provide an insightful view of the 2D COF (synthesized in the absence of atomic hydrogen) as the end point in an evolution of electronic structures from the monomer.