Patchett Ruth, Knighton Richard C, Mattock James D, Vargas Alfredo, Chaplin Adrian B
Department of Chemistry, University of Warwick , Gibbet Hill Road, Coventry CV4 7AL, U.K.
Department of Chemistry, School of Life Sciences, University of Sussex , Brighton BN1 9QJ, U.K.
Inorg Chem. 2017 Nov 20;56(22):14345-14350. doi: 10.1021/acs.inorgchem.7b02441. Epub 2017 Nov 2.
The synthesis of cationic rhodium and iridium complexes of a bis(imidazole-2-thione)-functionalized calix[4]arene ligand and their surprising capacity for potassium binding are described. In both cases, uptake of the alkali metal into the calix[4]arene cavity occurs despite adverse electrostatic interactions associated with close proximity to the transition-metal fragment [Rh···K = 3.715(1) Å; Ir···K = 3.690(1) Å]. The formation and constituent bonding of these unusual heterobimetallic adducts have been interrogated through extensive solution and solid-state characterization, examination of the host-guest chemistry of the ligand and its upper-rim unfunctionalized calix[4]arene analogue, and use of density functional theory based energy decomposition analysis.
