Suchergebnisse

Herein, we describe the first on-surface preparation of porphyrin nanotapes (Por NTs) on a gold surface. Structural and electronic characterization reveals that the Por NTs carry one unpaired electron at each end, which leads to magnetic end states. This study provides an alternative and versatile route to the fabrication of Por NTs and a detailed atomic-scale characterization of their structural and electronic properties. ; Porphyrin nanotapes (Por NTs) are promising structures for their use as molecular wires thanks to a high degree of π-conjugation, low HOMO—LUMO gaps, and exceptional conductance. Such structures have been prepared in solution, but their on-surface synthesis remains unreported. Here, meso–meso triply fused Por NTs have been prepared through a two-step synthesis on Au(111). The diradical character of the on-surface formed building block PorA2, a phenalenyl π-extended ZnIIPor, facilitates intermolecular homocoupling and allows for the formation of laterally π-extended tapes. The structural and electronic properties of individual Por NTs are addressed, both on Au(111) and on a thin insulating NaCl layer, by high-resolution scanning probe microscopy/spectroscopy complemented by DFT calculations. These Por NTs carry one unpaired electron at each end, which leads to magnetic end states. Our study provides a versatile route towards Por NTs and the atomic-scale characterization of such tapes. ; This work was supported by the Swiss National Science Foundation under Grant No. 200020_182015, the European Union's Horizon 2020 research and innovation programme under grant agreement number 785219 (Graphene Flagship Core 2), the Office of Naval Research (N00014-18-1-2708), MINECO, CTQ2017-85393-P (Phthalophoto, T.T.), and PID2020-116490GB-I00 (Porphyrinoids, T.T., G.B.). IMDEA Nanociencia also acknowledges support from the "Severo Ochoa" Programme for Centres of Excellence in R&D (MINECO, Grant SEV-2016-0686). R.R. and N.L. are grateful for funding from the EU-FET Open H2020 Mechanics with Molecules project (grant 766864). ; Peer reviewed

Triangular zigzag nanographenes, such as triangulene and its π‐extended homologues, have received widespread attention as organic nanomagnets for molecular spintronics, and may serve as building blocks for high‐spin networks with long‐range magnetic order, which are of immense fundamental and technological relevance. As a first step towards these lines, we present the on‐surface synthesis and a proof‐of‐principle experimental study of magnetism in covalently bonded triangulene dimers. On‐surface reactions of rationally designed precursor molecules on Au(111) lead to the selective formation of triangulene dimers in which the triangulene units are either directly connected through their minority sublattice atoms, or are separated via a 1,4‐phenylene spacer. The chemical structures of the dimers have been characterized by bond‐resolved scanning tunneling microscopy. Scanning tunneling spectroscopy and inelastic electron tunneling spectroscopy measurements reveal collective singlet–triplet spin excitations in the dimers, demonstrating efficient intertriangulene magnetic coupling. ; This work was supported by the Swiss National Science Foundation (grant numbers 200020-182015 and IZLCZ2-170184), the NCCR MARVEL funded by the Swiss National Science Foundation (grant number 51NF40-182892), the European Union's Horizon 2020 research and innovation program (grant number 785219, Graphene Flagship Core 2), the Office of Naval Research (grant number N00014-18-1-2708), an ERC Consolidator grant (T2DCP, grant number 819698), the German Research Foundation (DFG) within the Cluster of Excellence Center for Advancing Electronics Dresden (cfaed) and EnhanceNano (grant number 391979941), the European Social Fund and the Federal State of Saxony (ESF-Project GRAPHD, TU Dresden), the Generalitat Valenciana and Fondo Social Europeo (grant number ACIF/2018/175), MINECO-Spain (grant number MAT2016-78625), and the Portuguese FCT (grant number UTAPEXPL/NTec/0046/2017).

Triangular zigzag nanographenes, such as triangulene and its π‐extended homologues, have received widespread attention as organic nanomagnets for molecular spintronics, and may serve as building blocks for high‐spin networks with long‐range magnetic order, which are of immense fundamental and technological relevance. As a first step towards these lines, we present the on‐surface synthesis and a proof‐of‐principle experimental study of magnetism in covalently bonded triangulene dimers. On‐surface reactions of rationally designed precursor molecules on Au(111) lead to the selective formation of triangulene dimers in which the triangulene units are either directly connected through their minority sublattice atoms, or are separated via a 1,4‐phenylene spacer. The chemical structures of the dimers have been characterized by bond‐resolved scanning tunneling microscopy. Scanning tunneling spectroscopy and inelastic electron tunneling spectroscopy measurements reveal collective singlet–triplet spin excitations in the dimers, demonstrating efficient intertriangulene magnetic coupling. ; This work was supported by the Swiss National Science Foundation (grant numbers 200020-182015 and IZLCZ2-170184), the NCCR MARVEL funded by the Swiss National Science Foundation (grant number 51NF40-182892), the European Union's Horizon 2020 research and innovation program (grant number 785219, Graphene Flagship Core 2), the Office of Naval Research (grant number N00014-18-1-2708), an ERC Consolidator grant (T2DCP, grant number 819698), the German Research Foundation (DFG) within the Cluster of Excellence Center for Advancing Electronics Dresden (cfaed) and EnhanceNano (grant number 391979941), the European Social Fund and the Federal State of Saxony (ESF-Project GRAPHD, TU Dresden), the Generalitat Valenciana and Fondo Social Europeo (grant number ACIF/2018/175), MINECO-Spain (grant number MAT2016-78625), and the Portuguese FCT (grant number UTAPEXPL/NTec/0046/2017).

Fractionalization is a phenomenon in which strong interactions in a quantum system drive the emergence of excitations with quantum numbers that are absent in the building blocks. Outstanding examples are excitations with charge e/3 in the fractional quantum Hall effect1,2, solitons in one-dimensional conducting polymers3,4 and Majorana states in topological superconductors5. Fractionalization is also predicted to manifest itself in low-dimensional quantum magnets, such as one-dimensional antiferromagnetic S = 1 chains. The fundamental features of this system are gapped excitations in the bulk6 and, remarkably, S = 1/2 edge states at the chain termini7,8,9, leading to a four-fold degenerate ground state that reflects the underlying symmetry-protected topological order10,11. Here, we use on-surface synthesis12 to fabricate one-dimensional spin chains that contain the S = 1 polycyclic aromatic hydrocarbon triangulene as the building block. Using scanning tunnelling microscopy and spectroscopy at 4.5 K, we probe length-dependent magnetic excitations at the atomic scale in both open-ended and cyclic spin chains, and directly observe gapped spin excitations and fractional edge states therein. Exact diagonalization calculations provide conclusive evidence that the spin chains are described by the S = 1 bilinear-biquadratic Hamiltonian in the Haldane symmetry-protected topological phase. Our results open a bottom-up approach to study strongly correlated phases in purely organic materials, with the potential for the realization of measurement-based quantum computation13. ; This work was supported by the Swiss National Science Foundation (grant numbers 200020-182015 and IZLCZ2-170184), the NCCR MARVEL funded by the Swiss National Science Foundation (grant number 51NF40-182892), the European Union's Horizon 2020 research and innovation program (grant number 881603, Graphene Flagship Core 3), the Office of Naval Research (N00014-18-1-2708), ERC Consolidator grant (T2DCP, grant number 819698), the German Research Foundation within the Cluster of Excellence Center for Advancing Electronics Dresden (cfaed) and EnhanceNano (grant number 391979941), the Basque Government (grant number IT1249-19), the Generalitat Valenciana (Prometeo2017/139), the Spanish Government (grant number PID2019-109539GB-C41), and the Portuguese FCT (grant number SFRH/BD/138806/2018). Computational support from the Swiss Supercomputing Center (CSCS) under project ID s904 is gratefully acknowledged.

Nanographenes with zigzag edges are predicted to manifest non-trivial π-magnetism resulting from the interplay of concurrent electronic effects, such as hybridization of localized frontier states and Coulomb repulsion between valence electrons. This provides a chemically tunable platform to explore quantum magnetism at the nanoscale and opens avenues towards organic spintronics. The magnetic stability in nanographenes is thus far greatly limited by the weak magnetic exchange coupling, which remains below the room-temperature thermal energy. Here, we report the synthesis of large rhombus-shaped nanographenes with zigzag peripheries on gold and copper surfaces. Single-molecule scanning probe measurements show an emergent magnetic spin singlet ground state with increasing nanographene size. The magnetic exchange coupling in the largest nanographene (C70H22, containing five benzenoid rings along each edge), determined by inelastic electron tunnelling spectroscopy, exceeds 100 meV or 1,160 K, which outclasses most inorganic nanomaterials and survives on a metal electrode. ; This work was supported by the Swiss National Science Foundation (grant nos. 200020-182015 and IZLCZ2-170184), NCCR MARVEL funded by the Swiss National Science Foundation (grant no. 51NF40-182892), the European Union's Horizon 2020 research and innovation programme (grant no. 785219, Graphene Flagship Core 2), the Office of Naval Research (N00014-18-1-2708), the Max Planck Society, Ministry of Science and Innovation of Spain (grant nos. PID2019-106114GB-I00 and PID2019-109539GB), Generalitat Valenciana and Fondo Social Europeo (grant no. ACIF/2018/175), MINECO-Spain (grant no. MAT2016-78625) and Portuguese FCT (grant no. UTAPEXPL/ NTec/0046/2017). Computational support from the Swiss Supercomputing Center (CSCS) under project ID s904 is gratefully acknowledged.