Ammonium Complexes of Orthoester Cryptands Are Inherently Dynamic and Adaptive

• Published in: Journal of the American Chemical Society 2019-06, Vol.141 (22), p.8868-8876
• Main Authors: Wang, Xiang, Shyshov, Oleksandr, Hanževački, Marko, Jäger, Christof M, von Delius, Max
• Format: Article
• Language: English
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.9b01350

Fluxional chemical species such as bullvalene have been a valuable source of inspiration and fundamental insight into the nature of chemical bonds. A supramolecular analogue of bullvalene, i.e., a “fluxional host–guest system”, in which the ensemble of a well-defined host and guest is engaged in continuous, degenerate constitutional rearrangements, is still elusive, however. Here, we report experimental and computational evidence for guest-induced dynamic covalent rearrangements in the ammonium complexes of self-assembled orthoester cryptands. This unique behavior is made possible by the ammonium guest playing a dual role: it is sufficiently acidic to initiate dynamic covalent exchange reactions at the orthoester bridgeheads, and as a hydrogen bond donor it acts as a supramolecular template, governing the outcome of a multitude of possible intra- and intermolecular rearrangement reactions. One particularly striking example of inherent dynamic behavior was observed in host–guest complex [NH4 +⊂o-Me2-2.1.1], which spontaneously rearranged into the larger and thermodynamically more stable complex [NH4 +⊂o-Me2-2.2.1], even though this process led to the formation of poor host o-Me2-1.1.1 as a consequence of the excess of one subcomponent (diethylene glycol; “1” in our nomenclature). These inherently adaptive host–guest networks represent a unique platform for exploring the interrelationship between kinetic and thermodynamic stability. For instance, as a result of optimal NH4 + binding, complex [NH4 +⊂o-Me2-2.2.1] was found to be thermodynamically stable (negligible intermolecular rearrangements over weeks), whereas computational studies indicate that the compound is far from kinetically stable (intramolecular rearrangements).