An Adaptive Resorcinarene Hemicarcerand

Abstract

A new resorcinarene‐based hemicarcerand was developed, exhibiting pronounced flexibility in size and shape to accommodate several guest molecules. With a series of seven hemicarceplexes, investigated via single‐crystal XRD, the cage molecule showed to align its guests to complement their electrostatic potentials and to adjust its dimensions, according to the guest molecule‘s demand. Though forming equimolar inclusion complexes with most guests, crystallization from chloroform, and benzonitrile produced hemicarceplexes with a guest/host ratio of 2 : 1, exhibiting packing coefficients as high as 91 %. In competition experiments, the hemicarcerand clearly favors p‐xylene over m‐xylene: The host shows to crystallize, solely incarcerating p‐xylene from a 1 : 1 mixture of the two xylenes, and also isolates p‐xylene from the mixture via amorphous precipitation.

A box-in-box supramolecular assembly for the highly selective recognition of natural, epigenetically and chemically modified cytosines in water

“…51 Ward et al reported a cubic coordination cage with packing coefficients of up to 87%, 52 while Dyker et al reported an adaptive resorcinarene hemicarcerand with packing coefficients as high as 91%. 53 In this study, SC4H exhibited the highest PC (over 100%) to fit the cavity of 1•(PF 6 ) 4 , with only the lower rim capable of sliding into the macrocycle.…”

Purely Covalent Molecular Cages and Containers for Guest Encapsulation

“…Bottom left to right: benzaldehyde (CCDC: 2047582), nitrobenzene (CCDC: 2047576), benzonitrile (CCDC: 2047580), chloroform (CCDC: 2047579). Comparison of calculated cavities . CCDC: Cambridge Crystallographic Data Centre numbers.…”

“…By way of example, the volume of the cavity in 116 changes from 197 to 154 Å 3 when toluene and chloroform guests are, respectively, encapsulated (Figure 37). 102 Martı ́nez, Saaidi, and co-workers showed that subtle differences in the functional groups that envelope the cavity of cages 117 and 118 play a key role in defining affinity to encapsulate a certain guest. This is nicely demonstrated in the encapsulation of organochlorine insecticide chlordecone 119 by 117 and 118.…”