Organic open-shell compounds are extraordinarily attractive materials for their use in molecular spintronics thanks to their long spin-relaxation times and structural flexibility. Porphyrins (Pors) have widely been used as molecular platforms to craft persistent open-shell structures through solution-based redox chemistry. However, very few examples of inherently openshell Pors have been reported, which are typically obtained through the fusion of non-Kekulé polyaromatic hydrocarbon moieties to the Por core. The inherent instability and low solubility of these radical species, however, requires the use of bulky substituents and multi-step synthetic approaches. On-surface synthesis has emerged as a powerful tool to overcome such limitations, giving access to structures that cannot be obtained through classical methods. Herein, we present a simple and straightforward method for the on-surface synthesis of phenalenyl-fused Pors using readily available molecular precursors. In a systematic study, we examine the structural and electronic properties of three surface-supported Pors, bearing zero, two (PorA2) and four (PorA4) meso-fused phenalenyl moieties. Through atomically resolved real-space imaging by scanning probe microscopy and high-resolution scanning tunneling spectroscopy combined with density functional theory (DFT) calculations, we unambiguously demonstrate a triplet ground state for PorA2 and a charge transfer induced open-shell character for the intrinsically closed-shell PorA4.
On‐surface synthesis offers a versatile approach to prepare novel carbon‐based nanostructures that cannot be obtained by conventional solution chemistry. Graphene nanoribbons (GNRs) have potential for a variety of applications. A key issue for their application in molecular electronics is in the fine‐tuning of their electronic properties through structural modifications, such as heteroatom doping or the incorporation of non‐benzenoid rings. In this context, the covalent fusion of GNRs and porphyrins (Pors) is a highly appealing strategy. Herein we present the selective on‐surface synthesis of a Por–GNR hybrid, which consists of two Pors connected by a short GNR segment. The atomically precise structure of the Por–GNR hybrid has been characterized by bond‐resolved scanning tunneling microscopy (STM) and noncontact atomic force microscopy (nc‐AFM). The electronic properties have been investigated by scanning tunneling spectroscopy (STS), in combination with DFT calculations, which reveals a low electronic gap of 0.4 eV.
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.
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