No abstract

The bistability of spin-crossover complexes on surfaces is of great interest for potential applications. Using x-ray absorption spectroscopy, we investigated the properties of [Fe(pypyr(CF 3) 2) 2 (phen)] (pypyr = 2-(2'-pyridyl)pyrrolide, phen = 1,10-phenanthroline), a vacuum-evaporable Fe(II) complex, in direct contact to a set of substrates. The electronic properties of these substrates range from metallic to semiconducting. While dissociation is observed on metal surfaces, efficient light-induced switching is realized on semimetallic and semiconducting surfaces. This indicates that the density of states of the substrate at the Fermi level plays a role for the integrity and functionality of the adsorbed compound. In an intermediate case, namely [Fe(pypyr(CF 3) 2) 2 (phen)] on graphene/Ni(111), functional and dissociated species are found to coexist. This result indicates that some previous studies may deserve to be reconsidered because the possibility of coexisting intact and fragmented spin-crossover complexes was neglected.

The spin crossover compound Fe­(H2B­(pyrazole)­(pyridylpyrazole))2 was investigated in detail on Ag(111) with scanning tunneling microscopy (STM). A large fraction of the deposited molecules condenses into gridlike tetramers. Two molecules of each tetramer may be converted between two states by current injection. We attribute this effect to a spin transition. This interpretation is supported by control experiments on the analogous, magnetically passive Zn compound that forms virtually identical tetramers but exhibits no switching. The switching yields were studied for various electron energies, and the resulting values exceed those reported from other SCO systems by 2 orders of magnitude. The other two molecules of a tetramer were immutable. However, they may be used as contacts for current injection that leads to conversion of one of their neighbors. This “remote” switching is fairly efficient with yields reduced by only one to two orders of magnitude compared to direct excitation of a switchable molecule. We present a model of the tetramer structure that reproduces key observations from the experiments. In particular, sterical blocking prevents spin crossover of two molecules of a tetramer. Density functional theory calculations show that the model indeed represents a minimum energy structure. They also reproduce STM images and corroborate a remote-switching mechanism that is based on electron transfer between molecules.

Molecular rotors have attracted considerable interest for their prospects in nanotechnology. However, their adsorption on supporting substrates, where they may be addressed individually, usually modifies their properties. Here, we investigate the switching of two closely related three-state rotors mounted on platforms on Au(111) using low-temperature scanning tunneling microscopy and density functional theory calculations. Being physisorbed, the platforms retain important gas-phase properties of the rotor. This simplifies a detailed analysis and permits, for instance, the identification of the vibrational modes involved in the rotation process. The symmetry provided by the platform enables active control of the rotation direction through electrostatic interactions with the tip and charged neighboring adsorbates. The present investigation of two model systems may turn out useful for designing platforms that provide directional rotation and for transferring more sophisticated molecular machines from the gas phase to surfaces.

The coordination sphere of the Fe(II) terpyridine complex 1 is rigidified by fourfold interlinking of both terpyridine ligands. Profiting from an octa‐aldehyde precursor complex, the ideal dimensions of the interlinking structures are determined by reversible Schiff‐base formation, before irreversible Wittig olefination provided the rigidified complex. Reversed‐phase HPLC enables the isolation of the all‐trans isomer of the Fe(II) terpyridine complex 1, which is fully characterized. While temperature independent low‐spin states were recorded with superconducting quantum interference device (SQUID) measurements for both, the open precursor 8 and the interlinked complex 1, evidence of the increased rigidity of the ligand sphere in 1 was provided by proton T2 relaxation NMR experiments. The ligand sphere fixation in the macrocyclized complex 1 even reaches a level resisting substantial deformation upon deposition on an Au(111) surface, as demonstrated by its pristine form in a low temperature ultra‐high vacuum scanning tunneling microscope experiment.