A water-soluble Xe@cryptophane-111 complex exhibits very high thermodynamic stability and a peculiar (129)Xe NMR chemical shift

Robert M Fairchild; Akil I Joseph; K Travis Holman; Heather A Fogarty; Thierry Brotin; Jean-Pierre Dutasta; Céline Boutin; Gaspard Huber; Patrick Berthault

doi:10.1021/ja1071515

A water-soluble Xe@cryptophane-111 complex exhibits very high thermodynamic stability and a peculiar (129)Xe NMR chemical shift

J Am Chem Soc. 2010 Nov 10;132(44):15505-7. doi: 10.1021/ja1071515.

Authors

Robert M Fairchild¹, Akil I Joseph, K Travis Holman, Heather A Fogarty, Thierry Brotin, Jean-Pierre Dutasta, Céline Boutin, Gaspard Huber, Patrick Berthault

Affiliation

¹ Department of Chemistry, Georgetown University, Washington, DC 20057, USA.

PMID: 20958059
DOI: 10.1021/ja1071515

Abstract

The known xenon-binding (±)-cryptophane-111 (1) has been functionalized with six [(η(5)-C(5)Me(5))Ru(II)](+) ([Cp*Ru](+)) moieties to give, in 89% yield, the first water-soluble cryptophane-111 derivative, namely [(Cp*Ru)(6)1]Cl(6) ([2]Cl(6)). [2]Cl(6) exhibits a very high affinity for xenon in water, with a binding constant of 2.9(2) × 10(4) M(-1) as measured by hyperpolarized (129)Xe NMR spectroscopy. The (129)Xe NMR chemical shift of the aqueous Xe@[2](6+) species (308 ppm) resonates over 275 ppm downfield of the parent Xe@1 species in (CDCl(2))(2) and greatly broadens the practical (129)Xe NMR chemical shift range made available by xenon-binding molecular hosts. Single crystal structures of [2][CF(3)SO(3)](6)·xsolvent and 0.75H(2)O@1·2CHCl(3) reveal the ability of the cryptophane-111 core to adapt its conformation to guests.