Spin dynamics in rare earth single molecule magnets from muSR and NMR in [TbPc2_{2}]0^{0} and [DyPc2_{2}]0^{0}

The spin dynamics in [TbPc$_{2}$]$^{0}$ and [DyPc$_{2}$]$^{0}$ single molecule magnets have been investigated by means of muon and nuclear spin-lattice relaxation rate measurements. The correlation time for the spin fluctuations was found to be close to 0.1 ms already at 50 K, about two orders of magnitude larger than the one previously found in other lanthanide based single molecule magnets. In [TbPc$_{2}$]$^{0}$ two different regimes for the spin fluctuations have been evidenced: a high temperature activated one involving spin fluctuations across a barrier $\Delta\simeq 880 K$ separating the ground and first excited states and a low temperature regime involving quantum fluctuations within the twofold degenerate ground-state. In [DyPc$_{2}$]$^{0}$ a high temperature activated spin dynamics is also evidenced which, however, cannot be explained in terms of a single spin-phonon coupling constant.Comment: 4 pages, 4 figure

Graphene Spintronic Devices with Molecular Nanomagnets.

The possibility to graft nano-objects directly on its surface makesgraphene particularly appealing for device and sensing applications. Here we reportthe design and the realization of a novel device made by a graphene nanoconstrictiondecorated with TbPc2 magnetic molecules (Pc = phthalocyananine), to electricallydetect the magnetization reversal of the molecules in proximity with graphene. Amagnetoconductivity signal as high as 20% is found for the spin reversal, revealing theuniaxial magnetic anisotropy of the TbPc2 quantum magnets. These results depict thebehavior of multiple-field-effect nanotransistors with sensitivity at the single-molecule level

Landau-Zener Transition in a Continuously Measured Single-Molecule Spin Transistor

We monitor the Landau-Zener dynamics of a single-ion magnet inserted into a spin-transistor geometry. For increasing field-sweep rates, the spin reversal probability shows increasing deviations from that of a closed system. In the low-conductance limit, such deviations are shown to result from a dephasing process. In particular, the observed behaviors are successfully simulated by means of an adiabatic master equation, with time averaged dephasing (Lindblad) operators. The time average is tentatively interpreted in terms of the finite time resolution of the continuous measurement

Synthesis, characterization, monolayer assembly and 2D lanthanide coordination of a linear terphenyl-di(propiolonitrile) linker on Ag(111)

As a continuation of our work employing polyphenylene-dicarbonitrile molecules and in particular the terphenyl derivative 1 (TDCN), we have synthesized a novel ditopic terphenyl-4,4"-di(propiolonitrile) (2) linker for the self-assembly of organic monolayers and metal coordination at interfaces. The structure of the organic linker 2 was confirmed by single crystal X-ray diffraction analysis (XRD). On the densely packed Ag(111) surface, the terphenyl-4,4"-di(propiolonitrile) linkers self-assemble in a regular, molecular chevron arrangement exhibiting a Moiré pattern. After the exposure of the molecular monolayer to a beam of Gd atoms, the propiolonitrile groups get readily involved in metal–ligand coordination interactions. Distinct coordination motifs evolve with coordination numbers varying between three and six for the laterally-bound Gd centers. The linker molecules retain an overall flat adsorption geometry. However, only networks with restricted local order were obtained, in marked contrast to previously employed, simpler polyphenylene-dicarbonitrile 1 linkers

Field-regulated switching of the magnetization of Co-porphyrin on graphene

Differentmagnetic couplingmechanisms have been identified for a fewmonolayers of Co-porphyrin molecules deposited on a graphene-covered Ni(111) single crystal. A relatively strong antiferromagnetic coupling of the first molecular layer via graphene to the Ni crystal in comparison to a weaker intermolecular coupling gives rise to a complex field-dependent response of this hybrid system. By continuously increasing the magnetic field strength, the net magnetization of the molecular system switches from antiparallel to parallel to the field direction at 2.5 T. Utilizing x-ray absorption spectroscopy and x-ray magnetic circular dichroism, the element-specific magnetization and field dependence was probed. The nature of the magnetic couplings is identified by means of density functional theory and orbital-dependent susceptibilities

Spin-communication channels between Ln(III) bis-phthalocyanines molecular nanomagnets and a magnetic substrate

Learning the art of exploiting the interplay between different units at the atomic scale is a fundamental step in the realization of functional nano-architectures and interfaces. In this context, understanding and controlling the magnetic coupling between molecular centers and their environment is still a challenging task. Here we present a combined experimental-theoretical work on the prototypical case of the bis(phthalocyaninato)-lanthanide(III) (LnPc 2) molecular nanomagnets magnetically coupled to a Ni substrate. By means of X-ray magnetic circular dichroism we show how the coupling strength can be tuned by changing the Ln ion. The microscopic parameters of the system are determined by ab-initio calculations and then used in a spin Hamiltonian approach to interpret the experimental data. By this combined approach we identify the features of the spin communication channel: the spin path is first realized by the mediation of the external (5d) electrons of the Ln ion, keeping the characteristic features of the inner 4 f orbitals unaffected, then through the organic ligand, acting as a bridge to the external world

New Organic Electrode Materials for Ultrafast Electrochemical Energy Storage

Organic materials are both environmentally and economically attractive as potential electrode candidates. This Research News reports on a new class of stable and electrically conductive organic electrodes based on metal porphyrins with functional groups that are capable of electrochemical polymerization, rendering the materials promising for electrochemical applications. Their structural flexibility and the unique highly conjugated macrocyclic structure allows the produced organic electrodes to act as both cathode and anode materials giving access to fast charging as well as high cycling stability. The extreme thermal and chemical stability of the porphyrin‐based organic electrodes and their chemical versatility suggest an important role for these molecular systems in the further development of novel electrochemical energy storage applications

Surface-Confined Metal?Organic Nanostructures from Co-Directed Assembly of Linear Terphenyl-dicarbonitrile Linkers on Ag(111)

A detailed structural analysis of the surface supported self-assembly of terphenyl-4,4′′-dicarbonitrile molecules (NC−Ph3−CN) linked by Co adatoms on Ag(111) reveals different surface patterns depending on the constraints applied to the system. Without constraints, i.e., sufficient mobility and absence of space limitations at the surface, extended regular honeycomb nanomeshes are formed. On the basis of high-resolution scanning tunneling microscopy images, an atomistic model is derived showing the crystallographic orientation of the molecules and a commensurate alignment of the honeycomb networks, which exist in two rotational domains on the Ag(111) atomic lattice. For Co deficiency, an additional star-like Co-directed motif has been identified, and fully disordered networks are present if space limitations are imposed. In these cases, nodal motifs exist showing between 3- and 6-fold coordination of Co centers

Two-Dimensional 1,3,5-Tris(4-carboxyphenyl)benzene Self-Assembly at the 1-Phenyloctane/Graphite Interface Revisited

International audienceTwo-dimensional (2D) self-assembly of star-shaped 1,3,5-tris(4-carboxyphenyl)benzene molecules is investigated. Scanning tunneling microscopy reveals that this molecule can form three hydrogen-bonded networks at the 1-phenyloctane/graphite interface. One of these structures is close-packed and the two other ones are porous structures, with hexagonal and rectangular cavities. The network with rectangular cavities appears to be the most stable structure