Spin-state switching of transition-metal complexes (spin crossover) is sensitive to a variety of tiny perturbations. It is often found to be suppressed for molecules directly adsorbed on solid surfaces. We present X-ray absorption spectroscopy measurements of a submonolayer of [Fe(II)(NCS)2L] (L: 1-{6-[1,1-di(pyridin-2-yl)ethyl]-pyridin-2-yl}-N,N-dimethylmethanamine) deposited on a highly oriented pyrolytic graphite substrate in ultrahigh vacuum. These molecules undergo a thermally induced, fully reversible, gradual spin crossover with a transition temperature of T1/2 = 235(6) K and a transition width of ΔT80 = 115(8) K. Our results show that by using a carbon-based substrate the spin-crossover behavior can be preserved even for molecules that are in direct contact with a solid surface.
The competition of the free-spin state of a paramagnetic impurity on a superconductor with its screened counterpart is characterized by the energy scale of Kondo screening compared to the superconducting pairing energy Δ. When the experimental temperature suppresses Kondo screening, but preserves superconductivity, i.e., when Δ/k B > T > T K (k B is Boltzmann’s constant and T K the Kondo temperature), this description fails. Here, we explore this temperature range in a set of manganese phthalocyanine molecules decorated with ammonia on Pb(111). We show that these molecules suffice the required energy conditions by exhibiting weak-coupling Kondo resonances. We correlate the Yu-Shiba-Rusinov bound states energy inside the superconducting gap with the intensity of the Kondo resonance. The observed correlation follows the expectations for a classical spin on a superconductor. This finding is important in view of many theoretical predictions using a classical spin model, in particular for the description of Majorana bound states in magnetic nanostructures on superconducting substrates.
Efficient charge injection at organic semiconductor/metal interfaces is crucial for the performance of organic field effect transistors. Interfacial hybrid band formation between electronic states of the organic compound and the metal electrode facilitates effective charge injection. Here, we show that a long-range ordered monolayer of a flat-lying N-heteropolycyclic aromatic compound on Au(111) leads to dispersing occupied and unoccupied interfacial hybrid bands. Using angle-resolved two-photon photoemission we determine their energy level alignment and dispersion relations. We suggest that band formation proceeds via hybridization of a localized occupied molecular state with the d-bands of the Au substrate, where the large effective mass of the d-bands is significantly reduced in the hybrid band. Hybridization of an unoccupied molecular state with the Au sp-band leads to a band with an even smaller effective mass.
Surface-bound porphyrins are promising candidates for molecular switches, electronics and spintronics. Here, we studied the structural and the electronic properties of Fe-tetra-pyridil-porphyrin adsorbed on Au(111) in the monolayer regime. We combined scanning tunneling microscopy/spectroscopy, ultraviolet photoemission, and two-photon photoemission to determine the energy levels of the frontier molecular orbitals. We also resolved an excitonic state with a binding energy of 420 meV, which allowed us to compare the electronic transport gap with the optical gap.
The magnetic properties of metal-organic complexes are strongly influenced by conformational changes in the ligand. The flexibility of Fe-tetra-pyridyl-porphyrin molecules leads to different adsorption configurations on a Au(111) surface. By combining low-temperature scanning tunneling spectroscopy and atomic force microscopy, we resolve a correlation of the molecular configuration with different spin states and magnitudes of magnetic anisotropy. When the macrocycle exhibits a laterally-undistorted saddle shape, the molecules lie in a S=1 state with axial anisotropy arising from a square-planar ligand field. If the symmetry in the molecular ligand field is reduced by a lateral distortion of the molecule, we find a finite contribution of transverse anisotropy. Some of the distorted molecules lie in a S=2 state, again exhibiting substantial transverse anisotropy.
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