13C NMR of a single molecule magnet: analysis of pseudocontact shifts and residual dipolar couplings

Paramagnetic triple decker complexes of lanthanides are promising Single Molecule Magnets (SMMs), with many potential uses. Some of them show preferable relaxation behavior, which enables the recording of well resolved NMR spectra. These axially symmetric complexes are also strongly magnetically anisotropic, and this property can be described with the axial component of the magnetic susceptibility tensor, χa. For triple decker complexes with phthalocyanine based ligands, the Fermi˗contact contribution is small. Hence, together with the axial symmetry, the experimental chemical shifts in 1H and 13C NMR spectra can be modeled easily by considering pseudocontact and orbital shifts alone. This results in the determination of the χa value, which is also responsible for molecular alignment and consequently for the observation of residual dipolar couplings (RDCs). A detailed analysis of the experimental 1H-13C and 1H-1H couplings revealed that contributions from RDCs (positive and negative) and from dynamic frequency shifts (negative for all observed couplings) have to be considered. Whilst the pseudocontact shifts depend on the average positions of 1H and 13C nuclei relative to the lanthanide ions, the RDCs are related to the mobility of nuclei they correspond to. This phenomenon allows for the measurement of the internal mobility of the various groups in the SMMs.

Observations and modeling of the Marginal Ice Zone

Global climate change in recent decades has strongly influenced the Arctic generating pronounced warming accompanied by significant reduction of sea ice in seasonally ice-covered seas and a dramatic increase of open water regions exposed to wind [Stephenson et al., 2011]. By strongly scattering the wave energy, thick multiyear ice prevents swell from penetrating deeply into the Arctic pack ice. However, with the recent changes affecting Arctic sea ice, waves gain more energy from the extended fetch and can therefore penetrate further into the pack ice. Arctic sea ice also appears weaker during melt season, extending the transition zone between thick multi-year ice and the open ocean. This region is called the Marginal Ice Zone (MIZ). In the Arctic, the MIZ is mainly encountered in the marginal seas, such as the Nordic Seas, the Barents Sea, the Beaufort Sea and the Labrador Sea. Formed by numerous blocks of sea ice of various diameters (floes) the MIZ, under certain conditions, allows maritime transportation stimulating dreams of industrial and touristic exploitation of these regions and possibly allowing, in the next future, a maritime connection between the Atlantic and the Pacific. With the increasing human presence in the Arctic, waves pose security and safety issues. As marginal seas are targeted for oil and gas exploitation, understanding and predicting ocean waves and their effects on sea ice become crucial for structure design and for real time safety of operations. The juxtaposition of waves and sea ice represents a risk for personnel and equipment deployed on ice, and may complicate critical operations such as platform evacuations. The risk is difficult to evaluate because there are no long-term observations of waves in ice, swell events are difficult to predict from local conditions, ice breakup can occur on very short time-scales and wave-ice interactions are beyond the scope of current forecasting models [Liu and Mollo-Christensen, 1988,Marko, 2003]. In this thesis, a newly developed Waves in Ice Model (WIM) [Williams et al., 2013a,Williams et al., 2013b] and its related Ocean and Sea Ice model (OSIM) will be used to study the MIZ and the improvements of wave modeling in ice infested waters. The following work has been conducted in collaboration with the Nansen Environmental and Remote Sensing Center and within the SWARP project which aims to extend operational services supporting human activity in the Arctic by including forecast of waves in ice-covered seas, forecast of sea-ice in the presence of waves and remote sensing of both waves and sea ice conditions. The WIM will be included in the downstream forecasting services provided by Copernicus marine environment monitoring service.