Aggregation of Rare Earth Coordination Complexes in Solution Studied by Paramagnetic and DOSY NMR

Chemistry : a European Journal
Adeline W J PohDavid Parker

Abstract

The degree of aggregation of neutral, 9-coordinate rare earth coordination complexes has been shown to affect their ligand field, as revealed by diffusion-ordered NMR spectroscopy (DOSY-NMR) measurements on Y(III) complexes, paramagnetic NMR analyses of Yb and Tb analogues and emission spectral studies with the EuIII systems. In non-polar media a lipophilic tris-isopropyl complex, [Ln.L2 ] tends to aggregate in chloroform and dichloromethane giving rise to oligomers, whereas in acetic and trifluoroacetic acid the more polar parent complex, [Ln.L1 ], also aggregates, profoundly affecting the pseudocontact shift and the form of the Eu emission spectrum. Such behaviour has important implications in the design of responsive spectral probes.

References

Dec 18, 2013·Chemical Reviews·Marie C HeffernThomas J Meade
Feb 24, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Octavia A BlackburnSergey Shuvaev
Mar 16, 2016·Inorganic Chemistry·Goretti CastroLaura Valencia
Sep 9, 2017·Journal of the American Chemical Society·Michele VonciNicholas F Chilton

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