RESUMEN
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.
RESUMEN
Breaking a correlated pair in a superconductor requires an even number of fermions providing at least twice the pairing energy Δ. Here, we show that a single tunneling electron can also excite a pair breaking excitation in a proximitized gold film in the presence of magnetic impurities. Combining scanning tunneling spectroscopy with theoretical modeling, we map the excitation spectrum of an Fe-porphyrin molecule on the Au/V(100) proximitized surface into a manifold of entangled Yu-Shiba-Rusinov and spin excitations. Pair excitations emerge in the tunneling spectra as peaks outside the spectral gap only in the strong coupling regime, where the presence of a bound quasiparticle in the ground state ensures the even fermion parity of the excitation. Our results unravel the quantum nature of magnetic impurities on superconductors and demonstrate that pair excitations unequivocally reveal the parity of the ground state.
RESUMEN
Molecular spins on surfaces potentially used in quantum information processing and data storage require long spin excitation lifetimes. Normally, coupling of the molecular spin with the conduction electrons of metallic surfaces causes fast relaxation of spin excitations. However, the presence of superconducting pairing effects in the substrate can protect the excited spin from decaying. In this work, we show that a proximity-induced superconducting gold film can sustain spin excitations of a FeTPP-Cl molecule for more than 80 ns. This long value was determined by studying inelastic spin excitations of the S = 5/2 multiplet of FeTPP-Cl on Au films over V(100) using scanning tunneling spectroscopy. The spin lifetime decreases with increasing film thickness, along with the decrease of the effective superconducting gap. Our results elucidate the use of proximitized gold electrodes for addressing quantum spins on surfaces, envisioning new routes for tuning the value of their spin lifetime.