Guided Molecular Assembly on a Locally Reactive 2D Material.

Atomically precise engineering of the position of molecular adsorbates on surfaces of 2D materials is key to their development in applications ranging from catalysis to single-molecule spintronics. Here, stable room-temperature templating of individual molecules with localized electronic states on the surface of a locally reactive 2D material, silicene grown on ZrB2 , is demonstrated. Using a combination of scanning tunneling microscopy and density functional theory, it is shown that the binding of iron phthalocyanine (FePc) molecules is mediated via the strong chemisorption of the central Fe atom to the sp3 -like dangling bond of Si atoms in the linear silicene domain boundaries. Since the planar Pc ligand couples to the Fe atom mostly through the in-plane d orbitals, localized electronic states resembling those of the free molecule can be resolved. Furthermore, rotation of the molecule is restrained because of charge rearrangement induced by the bonding. These results highlight how nanoscale changes can induce reactivity in 2D materials, which can provide unique surface interactions for enabling novel forms of guided molecular assembly.

Controlling electronic access to the spin excitations of a single molecule in a tunnel junction.

Spintronic phenomena underpin new device paradigms for data storage and sensing. Scaling these down to the single molecule level requires controlling the properties of current-carrying molecular orbitals to enable access to spin states through phenomena such as inelastic electron tunnelling. Here we show that the spintronic properties of a tunnel junction containing a single molecule can be controlled using the local environment as a pseudo-gate. For tunnelling through iron phthalocyanine (FePc) on an insulating copper nitride (Cu2N) monolayer above Cu(001), we find that spin transitions may be strongly excited depending on the binding site of the central Fe atom. Different interactions between the Fe and the underlying Cu or N atoms shift the Fe d orbitals with respect to the Fermi energy and control the relative strength of the spin excitations; this effect is captured in a simple co-tunnelling model. This work demonstrates the importance of the atomic-scale environment for the development of single molecule spintronic devices.

Temperature- and Light-Induced Spin Crossover Observed by X-ray Spectroscopy on Isolated Fe(II) Complexes on Gold.

Using X-ray absorption techniques, we show that temperature- and light-induced spin crossover properties are conserved for a submonolayer of the [Fe(H2B(pz)2)2(2,2'-bipy)] complex evaporated onto a Au(111) surface. For a significant fraction of the molecules, we see changes in the absorption at the L2,3 edges that are consistent with those observed in bulk and thick film references. Assignment of these changes to spin crossover is further supported by multiplet calculations to simulate the X-ray absorption spectra. As others have observed in experiments on monolayer coverages, we find that many molecules in our submonolayer system remain pinned in one of the two spin states. Our results clearly demonstrate that temperature- and light-induced spin crossover is possible for isolated molecules on surfaces but that interactions with the surface may play a key role in determining when this can occur.