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Adaptive Behavior of Dynamic Orthoester Cryptands
Author(s) -
Shyshov Oleksandr,
Brachvogel RenéChris,
Bachmann Tobias,
Srikantharajah Rubitha,
Segets Doris,
Hampel Frank,
Puchta Ralph,
von Delius Max
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201609855
Subject(s) - cryptand , chemistry , orthoester , covalent bond , alkali metal , non covalent interactions , dynamic covalent chemistry , ion , computational chemistry , stereochemistry , molecule , supramolecular chemistry , organic chemistry , hydrogen bond
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.