A Molecular Capsule with Revolving Doors Partitioning Its Inner Space
| Autor: | Vageesha W. Liyana Gunawardana, Han Xie, Zhiquan Lei, Jovica D. Badjić, Radoslav Z. Pavlović, Curtis E. Moore, Tyler J. Finnegan |
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| Rok vydání: | 2020 |
| Předmět: | |
| Zdroj: | Chemistry – A European Journal. 26:16480-16485 |
| ISSN: | 1521-3765 0947-6539 |
| DOI: | 10.1002/chem.202003247 |
| Popis: | 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 A3 ) of 1 so that two equally sizeable compartments (190 A3 ) became joined through a conformationally flexible aromatic barrier. The compartments of such unique host could be populated with CCl4 (88 A3 ; PC=46 %), CBr4 (106 A3 ; 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. |
| Databáze: | OpenAIRE |
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