%0 Journal Article
%T A Molecular Capsule with Revolving Doors Partitioning Its Inner Space.
%A Lei Z
%A Finnegan TJ
%A Gunawardana VWL
%A Pavlović RZ
%A Xie H
%A Moore CE
%A Badjić JD
%J Chemistry
%V 26
%N 69
%D Dec 2020 9
%M 32648599
%F 5.02
%R 10.1002/chem.202003247
%X Covalent capsule 1 was designed to include two molecular baskets linked with three mobile pyridines tucked into its inner space. On the basis of both theory (DFT) and experiments (NMR and X-ray crystallography), we found that the pyridine "doors" split the chamber (380 Å3 ) of 1 so that two equally sizeable compartments (190 Å3 ) became joined through a conformationally flexible aromatic barrier. The compartments of such unique host could be populated with CCl4 (88 Å3 ; PC=46 %), CBr4 (106 Å3 ; 56 %) or their combination CCl4 /CBr4 (PC=51 %), with thermodynamic stabilities ΔG° tracking the values of packing coefficients (PC). Halogen (C-X⋅⋅⋅π) and hydrogen bonding (C-H⋅⋅⋅X) contacts held the haloalkane guests in the cavities of 1. The consecutive complexations were found to occur in a negative allosteric manner, which we propose to result from the induced-fit mode of complexation. Newly designed 1 opens a way for probing the effects of inner conformational dynamics on noncovalent interactions, reactivity and intramolecular translation in confined spaces of hollow molecules.