Open-shell polycyclic aromatic hydrocarbons (PAHs) represent promising building blocks for carbon-based functional magnetic materials. Their magnetic properties stem from the presence of unpaired electrons localized in radical states of π character. Consequently, these materials are inclined to exhibit spin delocalization, form extended collective states, and respond to the flexibility of the molecular backbones. However, they are also highly reactive, requiring structural strategies to protect the radical states from reacting with the environment. Here, we demonstrate that the open-shell ground state of the diradical 2-OS survives on a Au(111) substrate as a global singlet formed by two unpaired electrons with antiparallel spins coupled through a conformational-dependent interaction. The 2-OS molecule is a “protected” derivative of the Chichibabin’s diradical, featuring a nonplanar geometry that destabilizes the closed-shell quinoidal structure. Using scanning tunneling microscopy (STM), we localized the two interacting spins at the molecular edges, and detected an excited triplet state a few millielectronvolts above the singlet ground state. Mean-field Hubbard simulations reveal that the exchange coupling between the two spins strongly depends on the torsional angles between the different molecular moieties, suggesting the possibility of influencing the molecule’s magnetic state through structural changes. This was demonstrated here using the STM tip to manipulate the molecular conformation, while simultaneously detecting changes in the spin excitation spectrum. Our work suggests the potential of these PAHs as all-carbon spin-crossover materials.@en

Polycyclic aromatic hydrocarbons radicals are organic molecules with a nonzero total magnetic moment. Here, we report on charge-transport experiments with bianthracene-based radicals using a mechanically controlled break junction technique at low temperatures (6 K). The conductance spectra demonstrate that the magnetism of the diradical is preserved in solid-state devices and that it manifests itself either in the form of a Kondo resonance or inelastic electron tunneling spectroscopy signature caused by spin-flip processes. The magnetic fingerprints depend on the exact configuration of the molecule in the junction; this picture is supported by reference measurements on a radical molecule with the same backbone but with one free spin, in which only Kondo anomalies are observed. The results show that the open-shell structures based on the bianthracene core are interesting systems to study spin-spin interactions in solid-state devices, and this may open the way to control them either electrically or by mechanical strain.

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