title: Adaptive Behavior of Dynamic Orthoester Cryptands.
abstract: The integration of dynamic covalent bonds into macrocycles has been a tremendously successful strategy for investigating noncovalent interactions and identifying effective host-guest pairs. While numerous studies have focused on the dynamic responses of macrocycles and larger cages to various guests, the corresponding constitutionally dynamic chemistry of cryptands remains unexplored. Reported here is that cryptands based on orthoester bridgeheads offer an elegant entry to experiments in which a metal ion selects its preferred host from a dynamic mixture of competing subcomponents. In such dynamic mixtures, the alkali metal ions Li+, Na+, K+, Rb+, and Cs+exhibit pronounced preferences for the formation of cryptands of certain sizes and donor numbers, and the selection is rationalized by DFT calculations. Reported is also the first self-assembly of a chiral orthoester cryptate and a preliminary study on the use of stereoisomers as subcomponents.
authors.affiliation: Institute of Organic Chemistry and Advanced Materials, University of Ulm, Albert-Einstein-Allee 11, 89081, Ulm, Germany.
authors.forename: Oleksandr
authors.initials: O
authors.lastname: Shyshov
authors.affiliation: Institute of Organic Chemistry and Advanced Materials, University of Ulm, Albert-Einstein-Allee 11, 89081, Ulm, Germany.
authors.forename: René-Chris
authors.initials: RC
authors.lastname: Brachvogel
authors.affiliation: Department of Chemistry and Pharmacy, Institute of Organic Chemistry, and Computer Chemistry Center (CCC), Friedrich-Alexander Universität Erlangen-Nürnberg (FAU), Henkestrasse 42, 91054, Erlangen, Germany.
authors.forename: Tobias
authors.initials: T
authors.lastname: Bachmann
authors.affiliation: Institute of Particle Technology (LFG) and Interdisciplinary Center for Functional Particle Systems (FPS), Friedrich-Alexander Universität Erlangen-Nürnberg (FAU), Cauerstrasse 4, 91058, Erlangen, Germany.
authors.forename: Rubitha
authors.initials: R
authors.lastname: Srikantharajah
authors.affiliation: Institute of Particle Technology (LFG) and Interdisciplinary Center for Functional Particle Systems (FPS), Friedrich-Alexander Universität Erlangen-Nürnberg (FAU), Cauerstrasse 4, 91058, Erlangen, Germany.
authors.forename: Doris
authors.initials: D
authors.lastname: Segets
authors.affiliation: Department of Chemistry and Pharmacy, Institute of Organic Chemistry, and Computer Chemistry Center (CCC), Friedrich-Alexander Universität Erlangen-Nürnberg (FAU), Henkestrasse 42, 91054, Erlangen, Germany.
authors.forename: Frank
authors.initials: F
authors.lastname: Hampel
authors.affiliation: Department of Chemistry and Pharmacy, Institute of Organic Chemistry, and Computer Chemistry Center (CCC), Friedrich-Alexander Universität Erlangen-Nürnberg (FAU), Henkestrasse 42, 91054, Erlangen, Germany.
authors.forename: Ralph
authors.initials: R
authors.lastname: Puchta
authors.affiliation: Institute of Organic Chemistry and Advanced Materials, University of Ulm, Albert-Einstein-Allee 11, 89081, Ulm, Germany.
authors.forename: Max
authors.identifier: 0000-0003-1852-2969
authors.initials: M
authors.lastname: von Delius
keywords: NMR spectroscopy; cryptands; dynamic combinatorial chemistry; host-guest chemistry; supramolecular chemistry