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Reversibly controllable guest binding in precisely defined cavities: selectivity, induced fit, and switching in novel resorcin[4]arene-based container molecules

Gottschalk, T, Jarowski, PD and Diederich, F (2008) Reversibly controllable guest binding in precisely defined cavities: selectivity, induced fit, and switching in novel resorcin[4]arene-based container molecules Tetrahedron, 64, 36. pp. 8307-8317.

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Abstract

Two molecular baskets are presented, which were constructed based on a resorcin[4]arene platform. The molecules completely surround suitable guests, such as cyclo- or oxacycloalkanes, and bind them with high strength. The thermodynamic parameters for inclusion complexation were determined as well as the influence of encapsulation on the ring inversion barrier of bound cyclohexane. Two-dimensional NMR spectroscopy clearly shows the existence of a directed attractive interaction between oxacyclohexane and one of the hosts, which constrains the rotation of the bound molecule. Both containers exhibit remarkable binding selectivity as a consequence of their precisely defined structures. They both differentiate between homologous cycloalkanes, and whereas cyclohexane binds best within the larger of the two interior cavities, cyclopentane fits best in the smaller one. The selectivity is governed by ideal filling of space. We have conducted molecular dynamics experiments to understand the thermal fluctuations in the cavity sizes when a guest is bound. The simulations show that within a very narrow range the hosts adapt their binding site to different guests in order to optimize the fraction of occupied space. Once a binding geometry is established, it is characterized by a very low degree of flexibility. The guest-hosting properties of both molecules can be suspended by an external stimulus: addition of acid induces an opening of portals in the structures and immediately releases all bound cat-go. Neutralization of the solution completely restores the initial state. (C) 2008 Elsevier Ltd. All rights reserved.

Item Type: Article
Authors :
NameEmailORCID
Gottschalk, TUNSPECIFIEDUNSPECIFIED
Jarowski, PDp.d.jarowski@surrey.ac.ukUNSPECIFIED
Diederich, FUNSPECIFIEDUNSPECIFIED
Date : January 2008
Identification Number : https://doi.org/10.1016/j.tet.2008.04.102
Related URLs :
Depositing User : Symplectic Elements
Date Deposited : 17 May 2017 11:49
Last Modified : 17 May 2017 11:49
URI: http://epubs.surrey.ac.uk/id/eprint/832896

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