Organic radicals are promising candidates for molecular spintronics due to their intrinsic magnetic moment, their low spin-orbit coupling, and their weak hyperfine interactions. Using a mechanically controlled break junction setup at both room and low temperatures (6 K), we analyze the difference in charge transport between two nitronyl nitroxide radicals (NNR): one with a backbone in the para configuration, the other with a backbone in the meta configuration. We find that para-NNR displays a Kondo resonance at 6 K, while meta-NNR does not. Additionally, the observed Kondo peak in the differential conductance has a roughly constant width independent of the conductance, consistent with a scenario where the molecule is coupled asymmetrically to the electrodes.

In this thesis, we use methods offered by state of the art nanofabrication and single-molecule measurement techniques to capture polycyclic aromatic hydrocarbon (PAH) all-organic, di-radical molecules in solid-state devices, and study their electronic transport properties in different conditions with a focus on their magnetic properties.

Exploiting the potential of curcuminoids (CCMoids) as molecular platforms, a new 3.53 nm extended system (pyACCMoid, 2) has been designed in two steps by reacting a CCMoid with amino-terminal groups (NH2-CCMoid, 1, of 1.79 nm length) with polycyclic aromatic hydrocarbon (PAH) aldehydes. CCMoid 2 contains pyrene units at both ends as anchoring groups to optimize its trapping in graphene nano-junctions created by feedback-controlled electro-burning. The measured I–V characteristics show gate-dependent behaviour at room temperature and 10 K, with increased conductance values compared to shorter CCMoids previously reported, and in agreement with DFT calculations. Our results show that the adjusted molecular design improves the conductance, as system 2 separates the conductive backbone from the anchor groups, which tend to adopt a planar configuration upon contact with the graphene electrodes. DFT calculations using Green functions of a set of different molecular conformations of 2 on graphene electrodes show a direct relationship between the units (e.g. pyrene, amide, etc.), in the molecule, through which electrons are injected and the conductance values; where the size of the spacing between the graphene electrodes contributes but is not the dominant factor, and thus, counter-intuitively the smallest spacing gives one of the lowest conductance values.

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.

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.