Alkaline-earth metal cations as structure building blocks for molecular cages with entrapment and controlled release of quintuple ionic aggregates

Chemistry : a European Journal
Chi-Tsang WangKom-Bei Shiu

Abstract

Currently, main-group metal cations are totally neglected as the structure-building blocks for the self-assembly of supramolecular coordination metallocages due to the lack of directional bonding. However, here we show that a common Arrhenius acid-base neutralization allows the alkaline-earth metal cations to act as charged binders, easily connecting two or more highly directional anionic transition-metal-based metalloligands to coordination polymers. With a metal salt such as K(+) PF6 (-) added during the neutralization, the main-group metal-connected skeleton can be templated by the largest yet reported ionic-aggregate anion, K2 (PF6 )3 (-) , formed from KPF6 in solution, into molecular metallocages, encapsulating the ion. Crystal-structure details, DFT-calculation results, and controlled-release behavior support the presence of K2 (PF6 )3 (-) as a guest in the cage. Upon removal of PF6 (-) ions, the cage stays intact. Other ions like BF4 (-) can be put back in.

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Citations

Apr 4, 2017·Chemistry : a European Journal·Victoria E PritchardMichaele J Hardie
Jan 6, 2021·Journal of the American Chemical Society·David P AugustIñigo J Vitorica-Yrezabal

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