Crystal Structures of DOTMA Chelates from Ce3+ to Yb3+: Evidence for a Continuum of Metal Ion Hydration States

• Published in: Chemistry : a European journal 2019-07, Vol.25 (42), p.9997-10005
• Main Authors: Woods, Mark, Payne, Katherine M., Valente, Edward J., Kucera, Benjamin E., Young, Victor G.
• Format: Article
• Language: English
• Subjects: Cerium; Chelates; Chemistry; Coordination; coordination mode; Crystal structure; Dehydration; fractional coordination number; Gadolinium; Hydration; ionic radius; Ions; lanthanides; Ligands; Metal ions; Unit cell; Water chemistry
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201902068

The crystal structures of chelates formed between each stable paramagnetic lanthanide ion and the octadentate polyamino carboxylate ligand DOTMA are described. A total of 23 individual chelates structures were obtained; in each chelate the coordination geometry around the metal ion is best described as a twisted square antiprism (torsion angle −25.0°–−31.4°). Despite the uniformity of the general coordination geometry provided by the DOTMA ligand, there is a considerable variation in the hydration state of each chelate. The early Ln3+ chelates are associated with a single inner sphere water molecule; the Ln‐OH2 interaction is remarkable for being very long. After a clear break at gadolinium, the number of chelates in the unit cell that have a water molecule interacting with the Ln3+ decreases linearly until at Tm3+ no water is found to interact with the metal ion. The Ln‐OH2 distance observed in the chelates of the later Ln3+ ions are also extremely long and increase as the ions contract (2.550–2.732 Å). No clear break between hydrated and dehydrated chelates is observed; rather this series of chelates appear to represent a continuum of hydration states in which the ligand gradually closes around the metal ion as its ionic radius decreases (with decreased hydration) and the metal drops down into the coordination cage. Well‐coordinated: Loss of water from the inner coordination sphere of LnDOTMA chelates does not occur abruptly with decreasing Ln3+ size. Hydration decreases continuously from Tb3+ to Tm3+ until water is completely expelled from the metal.