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Paramagnetic polyoxometalates [RE 30 Co 8 Ge 12 W 108 O 408 (OH) 42 (OH 2 ) 30 ] 56- (Rare Earth (RE): Gd, Dy, Eu, and Y) are of special interest with regard to their application as alternative contrast agents in non-human magnetic resonance imaging which is increasingly used in materials science and process engineering. This class of new paramagnetic materials promises detailed findings in the magnetic resonance images due to their rather large total electron spin on the one hand, i.e. large, field-dependent relaxivities up to the highest magnetic fields, and due to their relatively large cluster sizes with an impact on adsorption and penetration on the other hand. Apart from the magnetic field dependence, the sensitivity of relaxivities to motional correlation times will be shown for these polyoxometalates which is a prerequisite for modelling and understanding the physical behaviour of this new class of polyoxometalates in MRI. Also for the qualitative and quantitative interpretation of MR images, the knowledge of transverse and longitudinal relaxivities of the paramagnetic clusters in a given environment is mandatory. Examples considered in this publication are proteins in milk fractionation, the deposit of which was measured by MRI.

With the aim to synthesize soluble cluster molecules, the silver salt of (4-( tert -butyl)phenyl)methanethiol [AgSCH 2 C 6 H 4 t Bu] was applied as a suitable precursor for the formation of a nanoscale silver sulfide cluster. In the presence of 1,6-(diphenylphosphino)hexane (dpph), the 115 nuclear silver cluster [Ag 115 S 34 (SCH 2 C 6 H 4 t Bu) 47 (dpph) 6 ] was obtained. The molecular structure of this compound was elucidated by single crystal X-ray analysis and fully characterized by spectroscopic techniques. In contrast to most of the previously published cluster compounds with more than a hundred heavy atoms, this nanoscale inorganic molecule is soluble in organic solvents, which allowed a comprehensive investigation in solution by UV-Vis spectroscopy and one- and two-dimensional NMR spectroscopy including 31 P/ 109 Ag-HSQC and DOSY experiments. These are the first heteronuclear NMR investigations on coinage metal chalcogenides. They give some first insight into the behavior of nanoscale silver sulfide clusters in solution. Additionally, molecular weight determinations were performed by 2D analytical ultracentrifugation and HR-TEM investigations confirm the presence of size-homogeneous nanoparticles present in solution.

In Magnetic Resonance Tomography (MRT) image contrast can be improved by adding paramagnetic relaxation agents such as lanthanide ions. Here we report on the use of highly paramagnetic isostructural Fe(III)/4f coordination clusters with a [Fe10Ln10] core to enhance relaxation. Measurements were performed over the range of (1)H Larmor frequencies of 10 MHz to 1.4 GHz in order to determine the relevant parameters for longitudinal and transverse relaxivities. Variation of the lanthanide ion allows differentiation of relaxation contributions from electronic states and molecular dynamics. We find that the transverse relaxivities increase with field, whereas the longitudinal relaxivities depend on the nature of the lanthanide. In addition, the Gd(III) analogue was selected in particular to test the interaction with tissue observed using MRT. Studies on biofilms used in waste water treatment reveal that the behaviour of the high-spin clusters is different from what is observed for common relaxation agents with respect to the penetration into the biofilms. The Fe10Gd10 cluster adheres to the surface of the biofilm better than the commercial agent Gadovist.