Olaf Fuhr

Small Ti clusters for catalysis of hydrogen exchange in NaAlH4

Colloidal Ti has been synthesized following a method described in the literature. Extended x-ray absorption fine structure measurements indicate the presence of small colloidal entities, consisting of only a few core Ti atoms which are coordinated by O atoms from tetrahydrofuran (THF). The results can be explained by the proposed structure of Ti13 6THF, in which the Ti cluster has the shape of a distorted icosahedron. The Ti colloid was used to prepare a functional nanocomposite by ball-milling the clusters with NaAlH4. The nanocomposite showed superior hydrogen exchange kinetics when compared to the state of the art in the literature.

Spin Dynamics in the Negatively Charged Terbium (III) Bis-phthalocyaninato Complex

The experimental and theoretical study of the electron spin dynamics in the anionic form of a single-ion molecule magnet (SIMM), the bis-phthalocyaninato terbium (III) molecule [Pc(2)Tb](-)[TBA](+), has been addressed by means of solid state (1)H NMR spectroscopy. The magnetic properties of the caged Tb(3+) metal center were investigated in a series of diamagnetically diluted preparations, where the excess of tetrabutylamonium bromide ([TBA]Br)(n) salt was used as diamagnetic matrix complement. We found that a high temperature activated spin dynamics characterizes the systems, which involved phonon-assisted transitions among the crystal field levels in qualitative agreements with literature results. However, the activation barriers in these processes range from 641 cm(-1) for the diamagnetically diluted samples to 584 cm(-1) for those undiluted; thus, they exhibit barriers 2-3 times larger than witnessed in earlier (230 cm(-1)) reports (e.g., Ishikawa, N.; Sugita, M.; Ishikawa, T.; Koshihara, S.; Kaizu, Y. J. Am. Chem. Soc. 2003, 125, 8694-8695). At cryogenic temperatures, fluctuations are driven by tunneling processes between the m = +6 and -6 low-energy levels. We found that the barrier Delta and the tunneling rates change from sample to sample and especially the diamagnetically diluted [Pc(2)Tb](-) molecules appear affected by the samples magneto/thermal history. These observations emphasize that matrix arrangements around [Pc(2)Tb](-) can appreciably alter the splitting of the crystal field levels, its symmetry, and hence, the spin dynamics. Therefore, understanding how small differences in molecular surroundings (as for instance occurring by depositing on surfaces) can trigger substantial modifications in the SIMM property is of utmost importance for the effective operation of such molecules for single-molecule data storage, for example.

Synthesis and structures of magnesium alanate and two solvent adducts

Abstract A synthesis and purification method for Mg(AlH4)2 is presented, which is based on a metathesis reaction of NaAlH4 and MgCl2 in diethyl ether and subsequent purification procedure leading to a high yield of the monoether adduct of Mg(AlH4)2. After removal of the solvent, the alanate has been obtained as a nanocrystalline material with a yield of 81% and a purity of 95%. Crystal structures were determined and discussed for the solvent adducts Mg(AlH4)2·4THF and Mg(AlH4)2·Et2O. A proposition is made for the structure of Mg(AlH4)2.

Single-molecule magnetism in a pentacoordinate cobalt(II) complex supported by an antenna ligand.

Pentacoordinate complex [CoL(3)Cl2] with a tridentate antenna-like ligand L(3) forms a dimer held by short π-π stacking with head-to-head contacts at 3.4 Å. The direct-current (dc) magnetic susceptibility and magnetization data confirm weak ferromagnetic interaction and a large-magnetic anisotropy, D/hc = 150 cm(-1) and E/hc = 11.6 cm(-1). The system shows superparamagnetic behavior at low temperature that depends upon the applied magnetic field. At Bdc = 0.2 T, a low-frequency peak at the out-of-phase susceptibility is seen (ν ∼ 0.3 Hz), whereas the onset of the second peak appears at ν > 1500 Hz, indicating the existence of two slow relaxation processes.

Expanding the Coordination Cage: A Ruthenium(II)−Polypyridine Complex Exhibiting High Quantum Yields under Ambient Conditions

A mononuclear ruthenium(II) polypyridyl complex with an enlarged terpyridyl coordination cage was synthesized by the formal introduction of a carbon bridge between the coordinating pyridine rings. Structurally, the ruthenium(II) complex shows an almost perfect octahedral N6 coordination around the central Ru(II) metal ion. The investigation of the photophysical properties reveals a triplet metal-to-ligand charge transfer emission with an unprecedented quantum yield of 13% and a lifetime of 1.36 mus at room temperature and in the presence of air oxygen. An exceptional small energy gap between light absorption and light emission, or Stokes shift, was detected. Additionally, time-dependent density functional theory calculations were carried out in order to characterize the ground state and both the singlet and triplet excited states. The exceptional properties of the new compound open the perspective of exploiting terpyridyl-like ruthenium complexes in photochemical devices under ambient conditions.

The structure of magnesium alanate

Mg(AlH(4))(2) was produced as a nanocrystalline powder by metathesis of NaAlH(4) and MgCl(2). Starting with a structure estimation which was developed from an evaluation of FTIR data and comparison of structural properties of two solvent adducts, quantum chemical calculations were performed on the density functional theory (DFT) level. The calculated atomic positions were used to simulate an X-ray powder diffraction pattern, based on a trigonal unit cell. The simulated pattern was congruent to experimental data. Thus, magnesium alanate exhibits a CdI(2) layer structure, the layers being formed by Mg atoms occupying the Cd sites and AlH(4) tedrahedra occupying the sites of the iodine atoms in CdI(2).

Constructing single-chain magnets by supramolecular π-π stacking and spin canting: a case study on manganese(III) corroles.

A single-chain magnet (SCM) was constructed from manganese(III) 5,10,15-tris(pentafluorophenyl)corrole complex [Mn(III) (tpfc)] through supramolecular π-π stacking without bridging ligands. In the crystal structures, [Mn(tpfc)] molecules crystallized from different solvents, such as methanol, ethyl acetate, and ethanol, exhibit different molecular orientations and intermolecular π-π interaction or weak Mn⋅⋅⋅O interaction to form a supramolecular one-dimensional motif or dimer. These three complexes show very different magnetic behaviors at low temperature. Methanol solvate 1 shows obvious frequency dependence of out-of-phase alternating-current magnetic susceptibility below 2 K and a magnetization hysteresis loop with a coercive field of 400 Oe at 0.5 K. It is the first example of spin-canted supramolecular single-chain magnet due to weak π-π stacking interaction. By fitting the susceptibility data χ(M) T (20-300 K) of 1 with the spin Hamiltonian expression H = -2J Σ(i=1)(n-1) S(Ai) S(Ai+1) + D Σ(i) S((iZ)(2)), the intrachain magnetic coupling parameter transmitted by π-π interaction of -0.31 cm(-1) and zero field splitting parameter D of -2.59 cm(-1) are obtained. Ethyl acetate solvate 2 behaves as an antiferromagnetic chain without ordering or slow magnetic relaxation down to 0.5 K. The magnetic susceptibility data χ(M) T (20-300 K) of 2 was fitted by assuming the spin Hamiltonian H = -2JΣ(i=1)(n-1) S(Ai) S(Ai+1), and the intrachain antiferromagnetic coupling constant of -0.07 cm(-1) is much weaker than that of 1. Ethanol solvate 3 with a dimer motif shows field-induced single-molecule magnet like behavior below 2.5 K. The exchange coupling constant J within the dimer propagated by π-π interaction is -0.14 cm(-1) by fitting the susceptibility data χ(M) T (20-300 K) with the spin Hamiltonian H = -2J S(A) S(B) + β(S((A)g(A)) + S((B)g(B)))H. The present studies open a new way to construct SCMs from anisotropic magnetic single-ion units through weak intermolecular interactions in the absence of bridging ligands.

Bisamide based non-nucleophilic electrolytes for rechargeable magnesium batteries

Non-nucleophilic electrolytes with outstanding electrochemical performances for magnesium batteries have been synthesized through the reaction between a bisamide magnesium and a Lewis acid in an aprotic solvent. High anodic stability, good ionic conductivity, excellent cycling efficiency and the feasibility of the preparation make the in situ generated electrolyte very promising for the potential application in rechargeable magnesium batteries.

Tuning the spin-transition properties of pyrene-decorated 2,6-bispyrazolylpyridine based Fe(II) complexes.

Two 2,6-bispyrazolylpyridine ligands (bpp) were functionalized with pyrene moieties through linkers of different lengths. In the ligand 2,6-di(1H-pyrazol-1-yl)-4-(pyren-1-yl)pyridine (L1) the pyrene group is directly connected to the bpp moiety via a C-C single bond, while in the ligand 4-(2,6-di(1H-pyrazol-1-yl)pyridin-4-yl)benzyl-4-(pyren-1-yl)butanoate (L2) it is separated by a benzyl ester group involving a flexible butanoic chain. Subsequent complexation of Fe(II) salts revealed dramatic the influence of the nature of the pyrene substitution on the spin-transition behaviour of the resulting complexes. Thus, compound [Fe(L1)(2)](ClO(4))(2) (1) is blocked in its high spin state due to constraints caused by a strong intermolecular π-π stacking in its structure. On the other hand, the flexible chain of ligand L2 in compounds [Fe(L2)(2)](ClO(4))(2) (2) and [Fe(L2)(2)](BF(4))(2)·CH(3)CN·H(2)O (3) prevents structural constraints allowing for reversible spin transitions. Temperature-dependent studies of the photophysical properties of compound 3 do not reveal any obvious correlation between the fluorescence of the pyrene group and the spin state of the spin transition core.

Switching of a coupled spin pair in a single-molecule junction

Single-molecule spintronics investigates electron transport through magnetic molecules that have an internal spin degree of freedom. To understand and control these individual molecules it is important to read their spin state. For unpaired spins, the Kondo effect has been observed as a low-temperature anomaly at small voltages. Here, we show that a coupled spin pair in a single magnetic molecule can be detected and that a bias voltage can be used to switch between two states of the molecule. In particular, we use the mechanically controlled break-junction technique to measure electronic transport through a single-molecule junction containing two coupled spin centres that are confined on two Co(2+) ions. Spin-orbit configuration interaction methods are used to calculate the combined spin system, where the ground state is found to be a pseudo-singlet and the first excitations behave as a pseudo-triplet. Experimentally, these states can be assigned to the absence and occurrence of a Kondo-like zero-bias anomaly in the low-temperature conductance data, respectively. By applying finite bias, we can repeatedly switch between the pseudo-singlet state and the pseudo-triplet state.