Spin-State Switching of Spin-Crossover Complexes on Cu(111) Evidenced by Spin-Flip Spectroscopy.

Spin-crossover compounds can be switched between two stable states with different magnetic moments, conformations, electronic, and optical properties, which opens appealing perspectives for technological applications including miniaturization down to the scale of single molecules. Although control of the spin states is crucial their direct identification is challenging in single-molecule experiments. Here we investigate the spin-crossover complex [Fe(HB(1,2,4-triazol-1-yl)3)2] on a Cu(111) surface with scanning tunneling microscopy and density functional theory calculations. Spin crossover of single molecules in dense islands is achieved via electron injection. Spin-flip excitations are resolved in scanning tunneling spectra in a magnetic field enabling the direct identification of the molecular spin state, and revealing the existence of magnetic anisotropy in the HS molecules.

Spin-Crossover and Fragmentation of Fe(neoim)2 on Silver and Gold.

The neutral spin crossover complex Fe(neoim)2, neoim being the deprotonated form of the ionogenic ligand 2-(1H-imidazol-2-yl)-9-methyl-1,10-phenanthroline (neoimH), is investigated on the (111) surfaces of Au and Ag using scanning tunneling microscopy and density functional theory calculations. The complex sublimates and adsorbs intact on Ag(111), where it exhibits an electron-induced spin crossover. However, it fragments on Au. According to density functional theory calculations, the adsorbed complex is drastically distorted by the interactions with the substrates, in particular by van der Waals forces. Dispersion interaction is also decisive for the relative stabilities of the low- and high-spin states of the adsorbed complex. The unexpected instability of the complex on the gold substrate is attributed to enhanced covalent bonding of the fragments to the substrate.

Spin Crossover in a Cobalt Complex on Ag(111).

The Co-based complex [Co(H2 B(pz)(pypz))2 ] (py=pyridine, pz=pyrazole) deposited on Ag(111) was investigated with scanning tunneling microscopy at ≈5 K. Due to a bis(tridentate) coordination sphere the molecules aggregate mainly into tetramers. Individual complexes in these tetramers undergo reversible transitions between two states with characteristic image contrasts when current is passed through them or one of their neighbors. Two molecules exhibit this bistability while the other two molecules are stable. The transition rates vary linearly with the tunneling current and exhibit an intriguing dependence on the bias voltage and its polarity. We interpret the states as being due to S=1 /2 and 3 /2 spin states of the Co2+ complex. The image contrast and the orders-of-magnitude variations of the switching yields can be tentatively understood from the calculated orbital structures of the two spin states, thus providing first insights into the mechanism of electron-induced excited spin-state trapping (ELIESST).

Electron-Induced Spin-Crossover in Self-Assembled Tetramers.

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.

Iron in a Cage: Fixation of a Fe(II)tpy2 Complex by Fourfold Interlinking.

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.

Rotation of Ethoxy and Ethyl Moieties on a Molecular Platform on Au(111).

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.

Reversible coordination-induced spin-state switching in complexes on metal surfaces.

Molecular spin switches are attractive candidates for controlling the spin polarization developing at the interface between molecules and magnetic metal surfaces1,2, which is relevant for molecular spintronics devices3-5. However, so far, intrinsic spin switches such as spin-crossover complexes have suffered from fragmentation or loss of functionality following adsorption on metal surfaces, with rare exceptions6-9. Robust metal-organic platforms, on the other hand, rely on external axial ligands to induce spin switching10-14. Here we integrate a spin switching functionality into robust complexes, relying on the mechanical movement of an axial ligand strapped to the porphyrin ring. Reversible interlocked switching of spin and coordination, induced by electron injection, is demonstrated on Ag(111) for this class of compounds. The stability of the two spin and coordination states of the molecules exceeds days at 4 K. The potential applications of this switching concept go beyond the spin functionality, and may turn out to be useful for controlling the catalytic activity of surfaces15.