Matthias Bernien

Spin Crossover in a Vacuum-Deposited Submonolayer of a Molecular Iron(II) Complex

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.

Reversing the Thermal Stability of a Molecular Switch on a Gold Surface: Ring-Opening Reaction of Nitrospiropyran

The ring-opening/closing reaction between spiropyran (SP) and merocyanine (MC) is a prototypical thermally and optically induced reversible reaction. However, MC molecules in solution are thermodynamically unstable at room temperature and thus return to the parent closed form on short time scales. Here we report contrary behavior of a submonolayer of these molecules adsorbed on a Au(111) surface. At 300 K, a thermally induced ring-opening reaction takes place on the gold surface, converting the initial highly ordered SP islands into MC dimer chains. We have found that the thermally induced ring-opening reaction has an activation barrier similar to that in solution. However, on the metal surface, the MC structures turn out to be the most stable phase. On the basis of the experimentally determined molecular structure of each molecular phase, we ascribe the suppression of the back reaction to a stabilization of the planar MC form on the metal surface as a consequence of its conjugated structure and large electric dipole moment. The metal surface thus plays a crucial role in the ring-opening reaction and can be used to alter the stability of the two isomers.

Spin-Crossover Complex on Au(111): Structural and Electronic Differences Between Mono- and Multilayers

Submono-, mono- and multilayers of the Fe(II) spin-crossover (SCO) complex [Fe(bpz)2 (phen)] (bpz=dihydrobis(pyrazolyl)borate, phen=1,10-phenanthroline) have beenprepared by vacuum deposition on Au(111) substrates and investigated with near edge X-ray absorption fine structure (NEXAFS) spectroscopy and scanning tunneling microscopy (STM). As evidenced by NEXAFS, molecules of the second layer exhibit a thermal spin crossover transition, although with a more gradual characteristics than in the bulk. For mono- and submonolayers of [Fe(bpz)2 (phen)] deposited on Au(111) substrates at room temperature both NEXAFS and STM indicate a dissociation of [Fe(bpz)2 (phen)] on Au(111) into four-coordinate complexes, [Fe(bpz)2 ], and phen molecules. Keeping the gold substrate at elevated temperatures ordered monolayers of intact molecules of [Fe(bpz)2 (phen)] are formed which can be spin-switched by electron-induced excited spin-state trapping (ELIESST).

Ferromagnetic coupling of mononuclear Fe centers in a self-assembled metal-organic network on Au(111).

The magnetic state and magnetic coupling of individual atoms in nanoscale structures relies on a delicate balance between different interactions with the atomic-scale surroundings. Using scanning tunneling microscopy, we resolve the self-assembled formation of highly ordered bilayer structures of Fe atoms and organic linker molecules (T4PT) when deposited on a Au(111) surface. The Fe atoms are encaged in a three-dimensional coordination motif by three T4PT molecules in the surface plane and an additional T4PT unit on top. Within this crystal field, the Fe atoms retain a magnetic ground state with easy-axis anisotropy, as evidenced by x-ray absorption spectroscopy and x-ray magnetic circular dichroism. The magnetization curves reveal the existence of ferromagnetic coupling between the Fe centers.

Highly Efficient Thermal and Light-Induced Spin-State Switching of an Fe(II) Complex in Direct Contact with a Solid Surface

Spin crossover (SCO) complexes possess a bistable spin state that reacts sensitively to changes in temperature or excitation with light. These effects have been well investigated in solids and solutions, while technological applications require the immobilization and contacting of the molecules at surfaces, which often results in the suppression of the SCO. We report on the thermal and light-induced SCO of [Fe(bpz)2phen] molecules in direct contact with a highly oriented pyrolytic graphite surface. We are able to switch on the magnetic moment of the molecules by illumination with green light at T = 6 K, and off by increasing the temperature to 65 K. The light-induced switching process is highly efficient leading to a complete spin conversion from the low-spin to the high-spin state within a submonolayer of molecules. [Fe(bpz)2phen] complexes immobilized on weakly interacting graphite substrates are thus promising candidates to realize the vision of an optically controlled molecular logic unit for spintronic devices.

Magnetic Coupling of Porphyrin Molecules Through Graphene

X-ray magnetic circular dichroism (XMCD) measurements and density functional theory (DFT)+U calculations reveal an unexpected antiferromagnetic coupling between physisorbed paramagnetic Co-porphyrin molecules and a Ni surface, separated by a graphene layer. A positive magnetization at the Ni substrate atoms is mediated by graphene and induces a negative one at the Co site, despite only a very small overlap between macrocyclic π and graphene pz -orbitals.

Structural and magnetic properties of epitaxial Fe ∕ Co O bilayers on Ag(001)

We have investigated the magnetic coupling between a metallic ferromagnet and an oxidic antiferromagnet in epitaxial single-crystalline

Vacuum-evaporable spin-crossover complexes: physicochemical properties in the crystalline bulk and in thin films deposited from the gas phase

\mathrm{Fe}∕\mathrm{Co}\mathrm{O}

Iron porphyrin molecules on Cu(001): Influence of adlayers and ligands on the magnetic properties

bilayers on Ag(001) using x-ray absorption spectroscopy. Absorption spectra taken from bilayers with different amounts of deposited Fe show only a weak indication for the formation of Fe oxide at the

Controlling the magnetism of adsorbed metal-organic molecules

\mathrm{Fe}∕\mathrm{Co}\mathrm{O}