Disentangling electron- and electric field-induced ring-closing reactions in a diarylethene derivative on Ag(111)

Using scanning tunneling microscopy and spectroscopy we investigate the adsorption properties and ring-closing reaction of a diarylethene derivative (C5F-4Py) on a Ag(111) surface. We identify an electron-induced reaction mechanism, with a quantum yield varying from $10^{-14}-10^{-9}$ per electron upon variation of the bias voltage from $1-2$ V. We ascribe the drastic increase in switching efficiency to a resonant enhancement upon tunneling through molecular orbitals. Additionally, we resolve the ring-closing reaction even in the absence of a current passing through the molecule. In this case the electric-field can modify the reaction barrier, leading to a finite switching probability at 4.8 K. A detailed analysis of the switching events shows that a simple plate-capacitor model for the tip-surface junction is insufficient to explain the distance dependence of the switching voltage. Instead, describing the tip as a sphere is in agreement with the findings. We resolve small differences in the adsorption configuration of the closed isomer, when comparing the electron- and field-induced switching product

Visualizing intramolecular distortions as the origin of transverse magnetic anisotropy

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

Electronic structure of an iron porphyrin derivative on Au(1 1 1)

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(1 1 1) 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

Direct imaging of the induced‐fit effect in molecular self‐assembly

Molecular recognition is a crucial driving force for molecular self‐assembly. In many cases molecules arrange in the lowest energy configuration following a lock‐and‐key principle. When molecular flexibility comes into play, the induced‐fit effect may govern the self‐assembly. Here, the self‐assembly of dicyanovinyl‐hexathiophene (DCV6T) molecules, a prototype specie for highly efficient organic solar cells, on Au(111) by using low‐temperature scanning tunneling microscopy and atomic force microscopy is investigated. DCV6T molecules assemble on the surface forming either islands or chains. In the islands the molecules are straight—the lowest energy configuration in gas phase—and expose the dicyano moieties to form hydrogen bonds with neighbor molecules. In contrast, the structure of DCV6T molecules in the chain assemblies deviates significantly from their gas‐phase analogues. The seemingly energetically unfavorable bent geometry is enforced by hydrogen‐bonding intermolecular interactions. Density functional theory calculations of molecular dimers quantitatively demonstrate that the deformation of individual molecules optimizes the intermolecular bonding structure. The intermolecular bonding energy thus drives the chain structure formation, which is an expression of the induced‐fit effect

Mapping the perturbation potential of metallic and dipolar tips in tunneling spectroscopy on MoS2

Scanning tunneling spectroscopy requires the application of a potential difference between the sample and a tip. In metal-vacuum-metal junctions, one can safely assume that the potential is constant along the metallic substrate. Here, we show that the inhomogeneous shape of the electric potential has to be taken into account when probing spatially extended molecules on a decoupling layer. To this end, oligothiophene-based molecules were deposited on a monolayer of molybdenum disulfide (MoS2) on a Au(111) surface. By probing the delocalized molecular orbital along the thiophene backbone, we found an apparent intramolecular shift of the positive ion resonance, which can be ascribed to a perturbation potential caused by the tip. Using a simple model for the electrostatic landscape, we show that such a perturbation is caused by the inhomogeneity of the applied bias potential in the junction and may be further modified by an electric dipole of a functionalized tip. The two effects can be disentangled in tunneling spectra by probing the apparent energy shift of vibronic resonances along the molecular backbone. We suggest that extended molecules on MoS2 can be used as a sensor for the shape of the electrostatic potential of arbitrary tips

Correlation of vibrational excitations and electronic structure with submolecular resolution

The detection of vibrational excitations of individual molecules on surfaces by scanning tunneling spectroscopy does not obey strict selection rules but rather propensity rules. The experimental verification of these excitations is challenging because it requires the independent variation of specific parameters, such as the electronic structure, while keeping the vibrational modes the same. Here, we make use of the versatile self-assembled structures of Fe-tetra-pyridyl-porphyrin molecules on a Au(111) surface. These molecules exhibit different energy-level alignments of the frontier molecular orbitals, thus allowing the correlation of the electronic structure and detection of vibrations. We identify up to seven vibrational modes in the tunneling spectra of the molecules in some of the arrangements, whereas we observe none in other structures. We find that the presence of vibrational excitations and their distribution along the molecule correlate with the observation of energetically low-lying molecular states. This correlation allows the explanation of the different numbers of vibrational signatures for molecules embedded within different structures as well as the bias asymmetry of the vibrational intensities within an individual molecule. Our observations are in agreement with the resonant enhancement of vibrations by the virtual excitation of electronic states

Control of oxidation and spin state in a single-molecule junction

The oxidation and spin state of a metal–organic molecule determine its chemical reactivity and magnetic properties. Here, we demonstrate the reversible control of the oxidation and spin state in a single Fe porphyrin molecule in the force field of the tip of a scanning tunneling microscope. Within the regimes of half-integer and integer spin state, we can further track the evolution of the magnetocrystalline anisotropy. Our experimental results are corroborated by density functional theory and wave function theory. This combined analysis allows us to draw a complete picture of the molecular states over a large range of intramolecular deformations

Correlation of Kondo effect and molecular conformation of the acceptor molecule in the TTF-TCNE charge transfer complex

A Kondo resonance has been observed on purely organic molecules in several combinations of charge transfer complexes on a metal surface. It has been regarded as a fingerprint of the transfer of one electron from the donor to the extended π orbital of the acceptor's LUMO. Here, we investigate the stoichiometric checkerboard structure of tetrathiafulvalene (TTF) and tetracyanoethylene (TCNE) on a Au(1 1 1) surface using scanning tunneling and atomic force microscopy at 4.8 K. We find a bistable state of the TCNE molecules with distinct structural and electronic properties. The two states represent different conformations of the TCNE within the structure. One of them exhibits a Kondo resonance, whereas the other one does not, despite of both TCNE types being singly charged

π-radical formation by pyrrolic H abstraction of phthalocyanine molecules on molybdenum disulfide

For a molecular radical to be stable, the environment needs to be inert. Furthermore, an unpaired electron is less likely to react chemically when it is placed in an extended orbital. Here, we use the tip of a scanning tunneling microscope to abstract one of the pyrrolic hydrogen atoms from phthalocyanine (H2Pc) deposited on a single layer of molybdenum disulfide (MoS2) on Au(111). We show the successful dissociation reaction by current-induced three-level fluctuations reflecting the inequivalent positions of the remaining H atom in the pyrrole center. Tunneling spectroscopy reveals two narrow resonances inside the semiconducting energy gap of MoS2 with their spatial extent resembling the highest occupied molecular orbital (HOMO) of H2Pc. By comparison to simple density functional calculations of the isolated molecule, we show that these correspond to a single occupation of the Coulomb-split highest molecular orbital of HPc. We conclude that the dangling σ bond after N–H bond cleavage is filled by an electron from the delocalized HOMO. The extended nature of the HOMO together with the inert nature of the MoS2 layer favors the stabilization of this radical state