RESUMO
Spin crossover (SCO) complexes sensitively react on changes of the environment by a change in the spin of the central metallic ion making them ideal candidates for molecular spintronics. In particular, the composite of SCO complexes and ferromagnetic (FM) surfaces would allow spin-state switching of the molecules in combination with the magnetic exchange interaction to the magnetic substrate. Unfortunately, when depositing SCO complexes on ferromagnetic surfaces, spin-state switching is blocked by the relatively strong interaction between the adsorbed molecules and the surface. Here, the Fe(II) SCO complex [FeII (Pyrz)2 ] (Pyrz = 3,5-dimethylpyrazolylborate) with sub-monolayer thickness in contact with a passivated FM film of Co on Au(111) is studied. In this case, the molecules preserve thermal spin crossover and at the same time the high-spin species show a sizable exchange interaction of > 0.9 T with the FM Co substrate. These observations provide a feasible design strategy in fabricating SCO-FM hybrid devices.
RESUMO
Rare-earth based single-molecule magnets are promising candidates for magnetic information storage including qubits as their large magnetic moments are carried by localized 4f electrons. This shielding from the environment in turn hampers a direct electronic access to the magnetic moment. Here, we present the indirect readout of the Dy moment in Bis(phthalocyaninato)dysprosium (DyPc_{2}) molecules on Au(111) using milli-Kelvin scanning tunneling microscopy. Because of an unpaired electron on the exposed Pc ligand, the molecules show a Kondo resonance that is, however, split by the ferromagnetic exchange interaction between the unpaired electron and the Dy angular momentum. Using spin-polarized scanning tunneling spectroscopy, we read out the Dy magnetic moment as a function of the applied magnetic field, exploiting the spin polarization of the exchange-split Kondo state.
RESUMO
Functional molecular groups mounted on specific foot structures are ideal model systems to study intermolecular interactions, due to the possibility to separate the functionality and the adsorption mechanism. Here, we report on the rotational switching of a thioacetate group mounted on a tripodal tetraphenylmethane (TPM) derivative adsorbed in ordered islands on a Au(111) surface. Using low temperature scanning tunnelling microscopy, individual freestanding molecular groups of the lattice can be switched between two bistable orientations. The functional dependence of this rotational switching on the sample bias and tip-sample distance allows us to model the energy landscape of this molecular group as an electric dipole in the electric field of the tunnelling junction. As expected for the interaction of two dipoles, we found states of neighbouring molecules to be correlated.
RESUMO
We present a self-assembled template that consists of tetraphenylmethane derivatives and adopts a periodic lateral arrangement on a Au(111) surface with acetyl groups sticking out of the molecular film. By using the tip of a scanning tunneling microscope, these acetyl groups can be removed in a spatially controlled way without significantly affecting the remaining molecular assembly. The chemically modified molecules can be readily distinguished from the original ones such that information can be engraved in the molecular film. Both the modified nature of an individual molecule and the order of the molecular film are shown to persist at room temperature. The mesh size of this molecular graph paper can be tuned by varying the length of the molecular spacer so that writing and reading information on the nanoscale with variable letter sizes becomes possible.
RESUMO
The rotation of entire molecules or large moieties happens at 100 ps time scales and the transition process itself is experimentally inaccessible to scanning probe techniques. However, the reversible switching of a molecule between more than two metastable states allows to assign a rotational switching direction. Rotational switching is a phenomenon that is particularly interesting with regard to possible applications in molecular motors. In this work, single tetraphenylmethane molecules deposited on a Au(111) surface were studied in a low temperature scanning tunneling microscope (STM). These molecules comprise rotational axes mounted on a tripodal sulfur-anchored stand and with the STM tip, we were able to induce transitions between six rotational states of the molecular motif. We were able to identify critical parameters for the onset of rotational switching and to characterize the influence of the local environment. The subtle difference between fcc and hcp stacking and the rotational state of neighboring molecules clearly influence the population of the rotational states.
RESUMO
One promising route toward encoding information is to utilize the two stable electronic states of a spin crossover molecule. Although this property is clearly manifested in transport across single molecule junctions, evidence linking charge transport across a solid-state device to the molecular film's spin state has thus far remained indirect. To establish this link, we deploy materials-centric and device-centric operando experiments involving X-ray absorption spectroscopy. We find a correlation between the temperature dependencies of the junction resistance and the Fe spin state within the device's [Fe(H2B(pz)2)2(NH2-phen)] molecular film. We also factually observe that the Fe molecular site mediates charge transport. Our dual operando studies reveal that transport involves a subset of molecules within an electronically heterogeneous spin crossover film. Our work confers an insight that substantially improves the state-of-the-art regarding spin crossover-based devices, thanks to a methodology that can benefit device studies of other next-generation molecular compounds.